Detergent compositions comprising hydrotropes

ABSTRACT

The present invention relates to detergent compositions, especially liquid, granular and tablet forms of laundry detergent compositions, that comprise improved hydrotropes, wherein the hydrotropes are organic molecules in which two polar groups are separated from each other by at least 5 aliphatic carbon atoms; liquid compositions that contain such hydrotropes have a viscosity, dilution profile and dissolution behavior that render the product effective and convenient for use as a liquid laundry detergent composition.

This appl. is a 371 of PCT/US00/21570 Aug. 8, 2000 which claims benefitof provisional appl. 60/148,056, Aug, 10, 1999 and claims benefits ofprovisional 60/150,233 Aug. 23, 1999, which claims benefit ofprovisional 60/156,339 Sep. 27, 1999 which claims benefit of provisional60/156,340 Aug. 27, 1999 which claims benefit of provisional 60/188,123Mar. 9, 2000.

FIELD OF THE INVENTION

The present invention relates to detergent compositions, especiallyliquid, granular and tablet forms of laundry detergent compositions,that comprise improved hydrotropes, wherein the hydrotropes are organicmolecules in which two polar groups are separated from each other by atleast 5 aliphatic carbon atoms; liquid compositions that certain suchhydrotropes have a viscosity, dilution profile and dissolution behaviorthat render the product effective and convenient for use as a liquidlaundry detergent composition.

BACKGROUND OF THE INVENTION

In recent years, the popularity of detergent products is forms otherthan granular/powder has increased. These other forms include liquidsand tables.

Liquid laundry detergent products offer a number of advantages over dry,powdered or particulate laundry detergent products. Liquid laundrydetergent products are readily measurable, speedily dissolved in washwater, non-dusting, are capable of being easily applied in concentratedsolutions or dispersions to soiled areas on garments to be laundered andusually occupy less storage space than granular products. Additionally,liquid laundry detergents may have incorporated into their formulationsmaterials which would deteriorate in the drying operations employed inthe manufacture of particulate or granular laundry detergent products.Because liquid laundry detergents are usually considered to be moreconvenient to use than granular laundry detergents, they have foundsubstantial favor with consumers.

Despite the advantages of liquid detergent compositions, granularproducts retain numerous advantages. These advantages includeperformance, formulation capability, lower-cost packaging and higherproduct stability. The advantages of product stability and formulationcapability are derived in large from the nature granular admixtureswhere components can be individually stabilized and isolated intoparticles before being admixed with other particles. This physicalseparation in the final detergent composition allows the use ofmaterials that are potentially unstable in a composition such asbleaches, enzymes, etc.

It is well-known to make detergent compositions in tablet form bycompacting a granular detergent composition. Such tablets offer theconvenience to consumers of pre-measured detergent dosage without theinconvenience and untidiness of measuring a sufficient amount of agranular detergent composition for each wash. Such products also offerconsiderable convenience to those consumers who launder the clothesoutside or away from their residence (e.g. at a laundromat) because theconsumer is required to transport only precisely as much laundrydetergent as she or he needs for clothes laundering. Detergentcompositions may be made in tablet form by compacting detergentparticulates.

A disadvantage with conventional liquid detergent compositions has beencompatibility of ingredients. Laundry detergent components which may becompatible with each other in granular and/or tablet products, may tendto interact or react with each other in a liquid, especially in anaqueous liquid environment.

A disadvantage with conventional granular/powder detergent compositionshas been relatively poor dissolution, dispersion and solubilityperformance.

A disadvantage with conventional tablet detergent compositions has beenthe conflict between making the tablets sufficiently strong and durableto avoid breaking apart during manufacture, transportation and/orstorage, while at the same time making the tablets in a manner such thatthe tablets rapidly disintegrate upon contact with wash water.

Given the foregoing, there is a continuing need to provide/formulateliquid detergent compositions which have not only excellent cleaningperformance and compositional and physical stability but which also havea viscosity, dilution profile and dissolution behavior that render themuseful and convenient for use as a liquid laundry detergent composition;there is a continuing need to provide/formulate granular/powderdetergent compositions which have improved dissolution, dispersion andsolubility performance while maintaining the granular/powder detergent'sinherent formulation flexibility; and there is a continuing need toprovide/formulate tablet detergent compositions which are both strongand durable to resist breakage during manufacture, transportation and/orstorage, and which also disintegrate rapidly upon contact with washwater so that the components of the tablet can provide detersivebenefits during the wash process.

SUMMARY OF THE INVENTION

It has now been discovered in the present invention that the addition ofcertain hydrotropes to the detergent compositions of the presentinvention, such as aqueous or non-aqueous liquid laundry detergentcompositions, granular/powder laundry detergent compositions and/ortablet laundry detergent compositions, provides 1) a liquid detergentproduct that has a viscosity, dilution profile and dissolution behaviorthat render the product useful and convenient as a liquid laundrydetergent composition, and/or 2) a granular/powder detergent producthaving improved dispersion, dissolution and/or solubility performancewith the need to reduce surfactant levels compared to granular/powderdetergent products that lack such hydrotropes, and/or 3) a tabletdetergent product, wherein the hydrotropes are useful as binding agents,having improved strength and durability properties with excellentdisintegration and dissolution properties compared to tablet detergentproducts that lack such hydrotropes.

A. Liquid Products

The liquid detergent products containing these hydrotropes demonstrateexcellent cleaning performance, excellent compositional and physicalstability and favorable product rheological behavior. These certainhydrotropes may be most generally classified as organic molecules inwhich two polar groups are separated from each other by at least 5aliphatic carbon atoms.

The liquid detergent products may be aqueous or non-aqueous. In apreferred aspect of the present invention a nonaqueous liquid detergentcomprising a hydrotrope having two polar groups separated from eachother by at least 5 aliphatic carbon atoms as well as from about 49% toabout 99.95% by weight of the composition of a surfactant-containingnon-aqueous liquid phase and from about 1% to about 50% by weight of thecomposition of particulate material which is substantially insoluble insaid liquid phase and which is selected from peroxygen bleaching agents,bleach activators, organic detergent builders, inorganic alkalinitysources and combinations thereof, is provided.

B. Granular/Powder Products

The granular/powder detergent products containing these hydrotropesdemonstrate improved dispersion, dissolution and/or solubilityperformance with the need to reduce surfactant levels compared togranular/powder detergent products that lack such hydrotropes. Thesehydrotropes may be most generally classified as an organic moleculewhich has a first polar group and a second polar group separated fromeach other by at least 5 aliphatic carbon atoms.

C. Tablet Products

The detergent tablets prepared according to the present inventioncomprise a hydrotrope (“binding agent”) characterized in that thebinding agent may be most generally classified as an organic moleculewhich has a first polar group and a second polar group separated fromeach other by at least 5 aliphatic carbon atoms. The tablet detergentproducts exhibit improved strength and durability properties withexcellent disintegration and dissolution properties compared to tabletdetergent products that lack such hydrotropes.

All parts, percentages and ratios used herein are expressed as percentweight unless otherwise specified. All documents cited are, in relevantpart, incorporated herein by reference.

DETAILED DESCRIPTION OF THE INVENTION

Definitions

“Hydrotrope”—As used herein, “hydrotrope” generally means a compoundwith the ability to increase the solubilities, preferably aqueoussolubilities, of certain slightly soluble organic compounds, morepreferably “hydrotrope” is defined as follows (see S. E. Friberg and M.Chiu, J. Dispersion Science and Technology, 9(5&6), pages 443 to 457,(1988-1989)):

-   1. A solution is prepared comprising 25% by weight of the specific    compound and 75% by weight of water.-   2. Octanoic Acid is thereafter added to the solution in a proportion    of 1.6 times the weight of the specific compound in solution, the    solution being at a temperature of 20° Celsius. The solution is    mixed in a Sotax beaker with a stirrer with a marine propeller, the    propeller being situated at about 5 mm above the bottom of the    beaker, the mixer being set at a rotation speed of 200 rounds per    minute.-   3. The specific compound is hydrotrope if the the Octanoic Acid is    completely solubilised, i.e. if the solution comprises only one    phase, the phase being a liquid phase.

“Non-Aqueous” or “Anhydrous”—As used herein, “non-aqueous” or“anhydrous” are used synonymously and both describe a fluid in which thefree water content is less than about 1%.

“Polar Groups”—As used herein, “polar groups” refers to functionalgroups which have a permanent electric dipole moment that arises fromthe partial charges on atoms linked by polar bonds. The polar groupitself may be anionic or uncharged.

“Dissolution”—As used herein, “dissolution” refers to the rate at whichthe detergent product mixes with water and releases the activeingredients in the wash.

“Particles”—As used herein, the word “particles” means the entire sizerange of a detergent final product or component or the entire size rangeof discrete particles, agglomerates, or granules in a final detergentproduct or component admixture. It specifically does not refer to a sizefraction (i.e., representing less than 100% of the entire size range) ofany of these types of particles unless the size fraction represents 100%of a discrete particle in an admixture of particles. For each type ofparticle component in an admixture, the entire size range of discreteparticles of that type have the same or substantially similarcomposition regardless of whether the particles are in contact withother particles. For agglomerated components, the agglomeratesthemselves are considered as discrete particles and each discreteparticle may be comprised of a composite of smaller primary particlesand binder compositions.

“Geometric Mean Particle Diameter”—As used herein, the phrase “geometricmean particle diameter” means the geometric mass median diameter of aset of discrete particles as measured by any standard mass-basedparticle size measurement technique, preferably by dry sieving.

“Geometric Standard Deviation” or “Span”—As used herein, the phrase“geometric standard deviation” or “span” of a particle size distributionmeans the geometric breadth of the best-fitted log-normal function tothe above-mentioned particle size data which can be accomplished by theratio of the diameter of the 84.13 percentile divided by the diameter ofthe 50^(th) percentile of the cumulative distribution (D_(84.13)/D₅₀);See Gotoh et al, Powder Technology Handbook, pp. 6-11, Meral Dekker1997.

Hydrotropes

The hydrotropes described in this section are an essential component ofthe present detergent compositions.

It has been discovered in the present invention that the addition of ahydrotrope in which two polar groups are separated from each other by atleast 5, preferably 6, aliphatic carbon atoms. Examples of suitablepolar groups for inclusion in the hydrotrope include are hydroxyl andcarboxyl ions. Particularly preferred hydrotropes are selected from thegroup consisting of:

mixtures thereof.

Mixtures of these organic molecules or any number of hydrotropesmolecules which consist of two polar groups separated from each other byat least 5, preferably 6, aliphatic carbon atoms are also acceptable.1,4 Cyclo Hexane Di Methanol may be present in either its cisconfiguration, its trans configuration or a mixture of bothconfigurations.

A. Liquid Products

The present invention comprises liquid laundry detergent compositionswhich are either aqueous or non-aqueous and which are suitable for usein an automatic washing machine or for pretreating stains and spots ontextile or fabric articles prior to washing. The present liquid laundrydetergent compositions may comprise solely a surfactant-richliquid-phase or they may contain both a surfactant-rich liquid-phase andsolid particulate phase which is suspended in the liquid phase.Preferably, the surfactant-rich liquid-phase comprises the hydrotropes,and optionally organic diluents.

The hydrotropes of the present invention, when incorporated into liquidproducts of the present invention, provide the key ingredient to preventgelling and/or thickening of the liquid detergent compositions taughtherein.

Gelling has been previously observed in the liquid detergent productsprepared without the hydrotropes as defined in the present invention,when the products are first contacted and diluted with water. Withoutbeing limited by theory, it is believed that this gelling phenomenonresults from the surfactant system forming viscous surfactant phases(typically lamellar, spherulitic or hexagonal phases) at certainconcentrations of surfactants and water. A correlation has been foundbetween the viscosity of the product: water mixture in the criticaldilution range where gelling is observed, and the amount of viscoussurfactant phase formed.

In a preferable embodiment, the detergent compositions are non-aqueous,having a surfactant-rich non-aqueous liquid phase and having a solidparticulate phase suspended in said liquid phase. In this embodiment,the surfactant-containing, non-aqueous liquid phase will generallycomprise from about 49% to 99.95% by weight of the detergentcompositions herein. More preferably, this liquid phase issurfactant-structured and will comprise from about 52% to 98.9% byweight of the compositions. Most preferably, this non-aqueous liquidphase will comprise from about 55% to 70% by weight of the compositionsherein. Such a surfactant-containing liquid phase will frequently have adensity of from about 0.6 to 1.4 g/cc, more preferably from about 0.9 to1.3 g/cc.

Without being bound by theory, it is believed that the hydrotropesdescribed above prevent the formation of the viscous surfactant phasesformed upon dilution, because the hydrotrope can effectively interactwith the ordered, structured layers of surfactant molecules, disruptthem and promote the formation of isotropic low-viscosity surfactantphases.

These hydrotropes also provide other benefits for improving the rheologyof liquid detergent compositions. For example, it is often difficult toincorporate ethoxylated quaternized amine materials into detergentcompositions containing anionic surfactant because the ethoxylatedquaternized amine material causes the anionic surfactant to precipitateout of the liquid phase causing the liquid detergent composition tothicken considerably. Nonetheless, it is highly desirable to incorporatethese clay soil removal/anti-redeposition agents into a liquid detergentproduct because they provide important performance benefits. It has beendiscovered in the present invention that by including the hydrotropesdescribed above the anionic surfactant precipitation and the compositionthickening usually observed is avoided and a liquid detergentcomposition of desirable rheological properties is produced.

Ethoxylated quaternized amine materials are described in greater detailbelow.

Surfactant-Containing Liquid-Phase

The liquid phase of the liquid detergent compositions herein ispreferably formed from hydrotropes, nonionic and anionic surfactants,and one or more organic diluent.

Organic Diluents—The major component of the liquid phase of thedetergent compositions herein comprises one or more aqueous ornon-aqueous organic diluents. The organic diluents used in thisinvention may be either surface active liquids, i.e., surfactants, ornon-surfactant liquids referred to herein as solvents. The term“solvent” is used herein to connote the non-surfactant liquid portion ofthe compositions herein. While some of the essential and/or optionalcomponents of the compositions herein may actually dissolve in the“solvent”-containing liquid phase, other components will be present asparticulate material dispersed within the “solvent”-containing liquidphase. Thus the term “solvent” is not meant to require that the solventmaterial be capable of actually dissolving all of the detergentcomposition components added thereto.

The liquid diluent component will generally comprise from about 50% to90%, more preferably from about 50% to 80%, most preferably from about55% to 75%, of a structured, surfactant-containing liquid phase.Preferably the liquid phase of the compositions herein, will compriseboth liquid surfactants and non-surfactant solvents.

i) Surfactant Liquids—Suitable types of surfactant liquids which can beused to form the liquid phase of the compositions herein include thealkoxylated alcohols, ethylene oxide (EO)-propylene oxide (PO) blockpolymers, polyhydroxy fatty acid amides, alkylpolysaccharides, and thelike. Such normally liquid surfactants are those having an HLB rangingfrom 10 to 16. Most preferred of the surfactant liquids are the alcoholalkoxylate nonionic surfactants.

Alcohol alkoxylates are materials which correspond to the generalformula:R¹(C_(m)H_(2m)O)_(n)OHwherein R¹ is a C₈-C₁₆ alkyl group, m is from 2 to 4, and n ranges fromabout 2 to 12. Preferably R¹ is an alkyl group, which may be primary orsecondary, that contains from about 9 to 15 carbon atoms, morepreferably from about 10 to 14 carbon atoms. Preferably also thealkoxylated fatty alcohols will be ethoxylated materials that containfrom about 2 to 12 ethylene oxide moieties per molecule, more preferablyfrom about 3 to 10 ethylene oxide moieties per molecule.

The alkoxylated fatty alcohol materials useful in the liquid phase willfrequently have a hydrophilic-lipophilic balance (HLB) which ranges fromabout 3 to 17. More preferably, the HLB of this material will range fromabout 6 to 15, most preferably from about 8 to 15.

Examples of fatty alcohol alkoxylates useful in or as the liquid phaseof the compositions herein will include those which are made fromalcohols of 12 to 15 carbon atoms and which contain about 7 moles ofethylene oxide. Such materials have been commercially marketed under thetrade names Neodol 25-7 and Neodol 23-6.5 by Shell Chemical Company.Other useful Neodols include Neodol 1-5, an ethoxylated fatty alcoholaveraging 11 carbon atoms in its alkyl chain with about 5 moles ofethylene oxide; Neodol 23-9, an ethoxylated primary C₁₂-C₁₃ alcoholhaving about 9 moles of ethylene oxide and Neodol 91-10, an ethoxylatedC₉-C₁₁ primary alcohol having about 10 moles of ethylene oxide. Alcoholethoxylates of this type have also been marketed by Shell ChemicalCompany under the Dobanol tradename. Dobanol 91-5 is an ethoxylatedC₉-C₁₁ fatty alcohol with an average of 5 moles ethylene oxide andDobanol 25-7 is an ethoxylated C₁₂-C₁₅ fatty alcohol with an average of7 moles of ethylene oxide per mole of fatty alcohol.

Other examples of suitable ethoxylated alcohols include Tergitol 15-S-7and Tergitol 15-S-9 both of which are linear secondary alcoholethoxylates that have been commercially marketed by Union CarbideCorporation. The former is a mixed ethoxylation product of C₁₁ to C₁₅linear secondary alkanol with 7 moles of ethylene oxide and the latteris a similar product but with 9 moles of ethylene oxide being reacted.

Other types of alcohol ethoxylates useful in the present compositionsare higher molecular weight nonionics, such as Neodol 45-11, which aresimilar ethylene oxide condensation products of higher fatty alcohols,with the higher fatty alcohol being of 14-15 carbon atoms and the numberof ethylene oxide groups per mole being about 11. Such products havealso been commercially marketed by Shell Chemical Company.

If alcohol alkoxylate nonionic surfactant is utilized as part of theliquid phase in the detergent compositions herein, it will preferably bepresent to the extent of from about 1% to 60% of the compositionstructured liquid phase. More preferably, the alcohol alkoxylatecomponent will comprise about 5% to 40% of the structured liquid phase.Most preferably, an alcohol alkoxylate component will comprise fromabout 5% to 35% of the detergent composition structured liquid phase.Utilization of alcohol alkoxylate in these concentrations in the liquidphase corresponds to an alcohol alkoxylate concentration in the totalcomposition of from about 1% to 60% by weight, more preferably fromabout 2% to 40% by weight, and most preferably from about 5% to 25% byweight, of the composition.

Another type of surfactant liquid which may be utilized in thisinvention are the ethylene oxide (EO)— propylene oxide (PO) blockpolymers. Materials of this type are well known nonionic surfactantswhich have been marketed under the tradename Pluronic. These materialsare formed by adding blocks of ethylene oxide moieties to the ends ofpolypropylene glycol chains to adjust the surface active properties ofthe resulting block polymers. EO-PO block polymer nonionics of this typeare described in greater detail in Davidsohn and Milwidsky; SyntheticDetergents 7th Ed.; Longman Scientific and Technical (1987) at pp. 34-36and pp. 189-191 and in U.S. Pat. Nos. 2,674,619 and 2,677,700. All ofthese publications are incorporated herein by reference. These Pluronictype nonionic surfactants are also believed to function as effectivesuspending agents for the particulate material which is dispersed in theliquid phase of the detergent compositions herein.

Another possible type of surfactant liquid useful in the compositionsherein comprises polyhydroxy fatty acid amide surfactants. Materials ofthis type of nonionic surfactant are those which conform to the formula:

wherein R is a C₉₋₁₇ alkyl or alkenyl, p is from 1 to 6, and Z isglycityl derived from a reduced sugar or alkoxylated derivative thereof.Such materials include the C₁₂-C₁₈ N-methyl glucamides. Examples areN-methyl N-1-deoxyglucityl cocoamide and N-methyl N-1-deoxyglucityloleamide. Processes for making polyhydroxy fatty acid, amides are knowand can be found, for example, in Wilson, U.S. Pat. No. 2,965,576 andSchwartz, U.S. Pat. No. 2,703,798, the disclosures of which areincorporated herein by reference. The materials themselves and theirpreparation are also described in greater detail in Honsa, U.S. Pat. No.5,174,937, Issued Dec. 26, 1992, which patent is also incorporatedherein by reference.

The detergent compositions of the present invention may also containanionic, cationic, and/or amphoteric types. In a preferred embodiment,where the liquid phase is non-aqueous, the liquid phase is prepared bycombining the non-aqueous organic liquid diluents described in thepresent invention with a surfactant which is generally, but notnecessarily, selected to add structure to the non-aqueous liquid phaseof the detergent compositions herein. Structuring surfactants can be ofthe anionic, nonionic, cationic, and/or amphoteric types. Thus thesurfactants described below may be added for solely their surface-activeattributes or for those attributes as well as their structuring ability.

Preferred surfactants are the anionic surfactants such as the alkylsulfates, the alkyl polyalkxylate sulfates and the linear alkyl benzenesulfonates. Another common type of anionic surfactant material which maybe optionally added to the detergent compositions herein as structurantcomprises carboxylate-type anionics. Carboxylate-type anionics includethe C₁₀-C₁₈ alkyl alkoxy carboxylates (especially the EO 1 to 5ethoxycarboxylates) and the C₁₀-C₁₈ sarcosinates, especially oleoylsarcosinate. Yet another common type of anionic surfactant materialwhich may be employed as a structurant comprises other sulfonatedanionic surfactants such as the C₈-C₁₈ paraffin sulfonates and theC₈-C₁₈ olefin sulfonates. Structuring anionic surfactants will generallycomprise from about 1% to 30% by weight of the compositions herein.

As indicated, one preferred type of structuring anionic surfactantcomprises primary or secondary alkyl sulfate anionic surfactants. Suchsurfactants are those produced by the sulfation of higher C₈-C₂₀ fattyalcohols.

Conventional primary alkyl sulfate surfactants have the general formulaROSO₃—M⁺wherein R is typically a linear C₈-C₂₀ hydrocarbyl group, which may bestraight chain or branched chain, and M is a water-solubilizing cation.Preferably R is a C₁₀₋₁₄ alkyl, and M is alkali metal. Most preferably Ris about C₁₂ and M is sodium.

Conventional secondary alkyl sulfates, as described above, may also beutilized as a structuring anionic surfactant for the liquid phase of thecompositions herein.

If utilized, alkyl sulfates will generally comprise from about 1% to 30%by weight of the composition, more preferably from about 5% to 25% byweight of the composition. Non-aqueous liquid detergent compositionscontaining alkyl sulfates, peroxygen bleaching agents, and bleachactivators are described in greater detail in Kong-Chan et al.; WO96/10073; Published Apr. 4, 1996, which application is incorporatedherein by reference.

Another preferred type of anionic surfactant material which may beoptionally added to the non-aqueous cleaning compositions herein as astructurant comprises the alkyl polyalkoxylate sulfates. Alkylpolyalkoxylate sulfates are also known as alkoxylated alkyl sulfates oralkyl ether sulfates. Such materials are those which correspond to theformulaR²—(C_(m)H_(2m)O)_(n)—SO₃Mwherein R² is a C₁₀-C₂₂ alkyl group, m is from 2 to 4, n is from about 1to 15, and M is a salt-forming cation. Preferably, R² is a C₁₂-C₁₈alkyl, m is 2, n is from about 1 to 10, and M is sodium, potassium,ammonium, alkylammonium or alkanolammonium. Most preferably, R² is aC₁₂-C₁₆, m is 2, n is from about 1 to 6, and M is sodium. Ammonium,alkylammonium and alkanolammonium counterions are preferably avoidedwhen used in the compositions herein because of incompatibility withperoxygen bleaching agents.

If utilized, alkyl polyalkoxylate sulfates can also generally comprisefrom about 1% to 30% by weight of the composition, more preferably fromabout 5% to 25% by weight of the composition. Non-aqueous liquiddetergent compositions containing alkyl polyalkoxylate sulfates, incombination with polyhydroxy fatty acid amides, are described in greaterdetail in Boutique et al; PCT Application No. PCT/US96/04223, whichapplication is incorporated herein by reference.

The most preferred type of anionic surfactant for use as a structurantin the compositions herein comprises the linear alkyl benzene sulfonate(LAS) surfactants. In particular, such LAS surfactants can be formulatedinto a specific type of anionic surfactant-containing powder which isespecially useful for incorporation into the non-aqueous liquiddetergent compositions of the present invention. Such a powder comprisestwo distinct phases. One of these phases is insoluble in the non-aqueousorganic liquid diluents used in the compositions herein; the other phaseis soluble in the non-aqueous organic liquids. It is the insoluble phaseof this preferred anionic surfactant-containing powder which can bedispersed in the non-aqueous liquid phase of the preferred compositionsherein and which forms a network of aggregated small particles thatallows the final product to stablely suspend other additional solidparticulate materials in the composition.

Further descriptions of suitable surfactants, and methods for preparingsuch surfactants can be found in the copending application of Jay I.Kahn et al., entitled “Preparation of Nonaqueous, Particulate-containingLiquid Detergent Compositions with Surfactant-Structured Liquid Phase”,having P&G Case No. 6150, Ser. No. 09/202,964, filed on Dec. 23, 1998,which is hereby incorporated by reference.

Generally, the liquid surfactant can comprise from about 25% to 70% ofthe liquid phase of the compositions herein. More preferably, the liquidsurfactant will comprise from about 30% to 65% of a structured liquidphase. This corresponds to a liquid surfactant concentration in thetotal composition of from about 10% to 70% by weight, more preferablyfrom about 20% to 50% by weight, of the composition. The amount of totalliquid surfactant in the preferred surfactant-structured, non-aqueousliquid phase herein is as described above and will be further determinedby the type and amounts of other composition components and by thedesired composition properties.

ii) Non-surfactant Organic Solvents—The liquid phase of the detergentcompositions herein may also comprise one or more non-surfactant organicsolvents. Such non-surfactant liquids are preferably those of lowpolarity. For purposes of this invention, “low-polarity” liquids arethose which have little, if any, tendency to dissolve one of thepreferred types of particulate material used in the compositions herein,i.e., the peroxygen bleaching agents, sodium perborate or sodiumpercarbonate. Thus relatively polar solvents such as ethanol arepreferably not utilized. Suitable types of low-polarity solvents usefulin the liquid detergent compositions herein do include alkylene glycolmono lower alkyl ethers, lower molecular weight polyethylene glycols,lower molecular weight methyl esters and amides, and the like.

A preferred type of low-polarity solvent for use in the compositionsherein comprises the C₄-C₈ branched or straight chain alkylene glycols.Materials of this type include hexylene glycol(4-methyl-2,4-pentanediol), 1,3-butylene glycol and 1,4-butylene glycol.

Another preferred type of low-polarity solvent for use herein comprisesthe mono-, di-, tri-, or tetra-C₂-C₃ alkylene glycol mono C₂-C₆ alkylethers. The specific examples of such compounds include diethyleneglycol monobutyl ether, tetraethylene glycol monobutyl ether,dipropolyene glycol monoethyl ether, and dipropylene glycol monobutylether. Diethylene glycol monobutyl ether, dipropylene glycol monobutylether and butoxy-propoxy-propanol (BPP) are especially preferred.Compounds of the type have been commercially marketed under thetradenames Dowanol, Carbitol, and Cellosolve.

Another preferred type of low-polarity organic solvent useful hereincomprises the lower molecular weight polyethylene glycols (PEGs). Suchmaterials are those having molecular weights of at least about 150. PEGsof molecular weight ranging from about 200 to 600 are most preferred.

Yet another preferred type of non-polar solvent comprises lowermolecular weight methyl esters. Such materials are those of the generalformula: R¹—C(O)—OCH₃ wherein R¹ ranges from 1 to about 18. Examples ofsuitable lower molecular weight methyl esters include methyl acetate,methyl propionate, methyl octanoate, and methyl dodecanoate.

The generally low-polarity, non-surfactant organic solvent(s) employedshould, of course, be compatible and non-reactive with other compositioncomponents, e.g., bleach and/or activators, used in the liquid detergentcompositions herein. Such a solvent component is preferably utilized inan amount of from about 1% to 70% by weight of the liquid phase. Morepreferably, a low-polarity, non-surfactant solvent will comprise fromabout 10% to 60% by weight of a structured liquid phase, most preferablyfrom about 20% to 50% by weight, of a structured liquid phase of thecomposition. Utilization of non-surfactant solvent in theseconcentrations in the liquid phase corresponds to a non-surfactantsolvent concentration in the total composition of from about 1% to 50%by weight, more preferably from about 5% to 40% by weight, and mostpreferably from about 10% to 30% by weight, of the composition.

iii) Blends of Surfactant and Non-surfactant Solvents—In the preferredembodiments which employ both non-aqueous surfactant liquids andnon-aqueous non-surfactant solvents, the ratio of surfactant tonon-surfactant liquids, e.g., the ratio of alcohol alkoxylate to lowpolarity solvent, within a structured, surfactant-containing liquidphase can be used to vary the rheological properties of the detergentcompositions eventually formed. Generally, the weight ratio ofsurfactant liquid to non-surfactant organic solvent will range about50:1 to 1:50. More preferably, this ratio will range from about 3:1 to1:3, most preferably from about 2:1 to 1:2.

Solid Particulate Materials

In addition to the surfactant-containing liquid phase, the liquiddetergent compositions herein also preferably comprise from about 1% to50% by weight, more preferably from about 29% to 44% by weight, ofadditional solid phase particulate material which is dispersed andsuspended within the liquid phase. Generally such particulate materialwill range in size from about 0.1 to 1500 microns, more preferably fromabout 0.1 to 900 microns. Most preferably, such material will range insize from about 5 to 200 microns.

The additional particulate material utilized herein can comprise one ormore types of detergent composition components which in particulate formare substantially insoluble in the liquid phase of the composition. Suchmaterials include peroxygen bleaching agents, bleach activators, organicdetergent builders, inorganic alkalinity sources and combinationsthereof. The types of particulate materials which can be utilized aredescribed in detail, below, as follows, however, some materials caneither be included in the particulate component or in thesurfactant-containing liquid phase.

In a preferred embodiment the particulate material comprises the dyetransfer inhibitor PVNO (see above for detailed description), analuminosilicate detergent builder as well as other particulate minorcomponents.

(a) Bleaching Agent With Optional Bleach Activators—The most preferredtype of particulate material useful in the detergent compositions hereincomprises particles of a peroxygen bleaching agent. Such peroxygenbleaching agents may be organic or inorganic in nature. Inorganicperoxygen bleaching agents are frequently utilized in combination with ableach activator.

Useful organic peroxygen bleaching agents include percarboxylic acidbleaching agents and salts thereof. Suitable examples of this class ofagents include magnesium monoperoxyphthalate hexahydrate, the magnesiumsalt of metachloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acidand diperoxydodecanedioic acid. Such bleaching agents are disclosed inU.S. Pat. No. 4,483,781, Hartman, Issued Nov. 20, 1984; European PatentApplication EP-A-133,354, Banks et al., Published Feb. 20, 1985; andU.S. Pat. No. 4,412,934, Chung et al., Issued Nov. 1, 1983. Highlypreferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproicacid (NAPAA) as described in U.S. Pat. No. 4,634,551, Issued Jan. 6,1987 to Burns et al.

Inorganic peroxygen bleaching agents may also be used in particulateform in the detergent compositions herein. Inorganic bleaching agentsare in fact preferred. Such inorganic peroxygen compounds include alkalimetal perborate and percarbonate materials, most preferably thepercarbonates. For example, sodium perborate (e.g. mono- ortetra-hydrate) can be used. Suitable inorganic bleaching agents can alsoinclude sodium or potassium carbonate peroxyhydrate and equivalent“percarbonate” bleaches, sodium pyrophosphate peroxyhydrate, ureaperoxyhydrate, and sodium peroxide. Persulfate bleach (e.g., OXONE,manufactured commercially by DuPont) can also be used. Frequentlyinorganic peroxygen bleaches will be coated with silicate, borate,sulfate or water-soluble surfactants. For example, coated percarbonateparticles are available from various commercial sources such as FMC,Solvay Interox, Tokai Denka and Degussa.

Inorganic peroxygen bleaching agents, e.g., the perborates, thepercarbonates, etc., are preferably combined with bleach activators,which lead to the in situ production in aqueous solution (i.e., duringuse of the compositions herein for fabric laundering/bleaching) of theperoxy acid corresponding to the bleach activator. Various non-limitingexamples of activators are disclosed in U.S. Pat. No. 4,915,854, IssuedApr. 10, 1990 to Mao et al.; and U.S. Pat. No. 4,412,934 Issued Nov. 1,1983 to Chung et al. The nonanoyloxybenzene sulfonate (NOBS) andtetraacetyl ethylene diamine (TAED) activators are typical. Mixturesthereof can also be used. See also the hereinbefore referenced U.S. Pat.No. 4,634,551 for other typical bleaches and activators useful herein.

Other useful amido-derived bleach activators are described in U.S. Pat.No. 5,891,838, issued Apr. 6, 1999 to Angell et al., and the copendingprovisional application of Diane Parry entitled “Non-aqueous, LiquidDetergent Compositions Containing Gasified Particulate Matter,” P&G CaseNo. 7173P, Ser. No. 60/088,170 filed Jun. 5, 1998, both of which ishereby incorporated by reference.

If peroxygen bleaching agents are used as all or part of the additionalparticulate material, they will generally comprise from about 1% to 30%by weight of the composition. More preferably, peroxygen bleaching agentwill comprise from about 1% to 20% by weight of the composition. Mostpreferably, peroxygen bleaching agent will be present to the extent offrom about 5% to 20% by weight of the composition. If utilized, bleachactivators can comprise from about 0.5% to 20%, more preferably fromabout 3% to 10%, by weight of the composition. Frequently, activatorsare employed such that the molar ratio of bleaching agent to activatorranges from about 1:1 to 10:1, more preferably from about 1.5:1 to 5:1.

(b) Transition Metal Bleach Catalysts—Another possible type ofadditional particulate material which can be suspended in the liquiddetergent compositions herein comprises transition metal bleachcatalysts which encourage the catalytic oxidation of soils and stains onfabric surfaces. Such compounds are present in a catalytically effectiveamount, preferably from about 1 ppb to about 99.9%, more typically fromabout 0.001 ppm to about 49%, preferably from about 0.05 ppm to about500 ppm (wherein “ppb” denotes parts per billion by weight and “ppm”denotes parts per million by weight), of a laundry detergentcomposition. The transition-metal bleach catalyst comprises a complex ofa transition metal selected from the group consisting of Mn(II),Mn(III), Mn(IV), Mn(V), Fe(II), Fe(III), Fe(IV), Co(I), Co(II), Co(III),Ni(I), Ni(II), Ni(III), Cu(I), Cu(II), Cu(III), Cr(II), Cr(III), Cr(IV),Cr(V), Cr(VI), V(III), V(IV), V(V), Mo(IV), Mo(V), Mo(VI), W(IV), W(V),W(VI), Pd(II), Ru(II), Ru(III), and Ru(IV) coordinated with amacropolycyclic rigid ligand, preferably a cross-bridged macropolycyclicligand, having at least 4 donor atoms, at least two of which arebridgehead donor atoms. These catalysts are discussed with greaterspecificity in the copending provisional application of Daryle H. Buschet al., entitled “Catalysts and Methods for Catalytic Oxidation”, havingP&G Case No. 6524P, Ser. No. 60/040,629, which is hereby incorporated byreference.

(c) Organic Builder Material—Another possible type of additionalparticulate material which can be suspended in the liquid detergentcompositions herein comprises an organic detergent builder materialwhich serves to counteract the effects of calcium, or other ion, waterhardness encountered during laundering/bleaching use of the compositionsherein. Examples of such materials include the alkali metal, citrates,succinates, malonates, fatty acids, carboxymethyl succinates,carboxylates, polycarboxylates and polyacetyl carboxylates. Specificexamples include sodium, potassium and lithium salts of oxydisuccinicacid, mellitic acid, benzene polycarboxylic acids and citric acid. Otherexamples of organic phosphonate type sequestering agents such as thosewhich have been sold by Monsanto under the Dequest tradename andalkanehydroxy phosphonates. Citrate salts are highly preferred.

Other suitable organic builders include the higher molecular weightpolymers and copolymers known to have builder properties. For example,such materials include appropriate polyacrylic acid, polymaleic acid,and polyacrylic/polymaleic acid copolymers and their salts, such asthose sold by BASF under the Sokalan trademark which have molecularweight ranging from about 5,000 to 100,000.

Another suitable type of organic builder comprises the water-solublesalts of higher fatty acids, i.e., “soaps”. These include alkali metalsoaps such as the sodium, potassium, ammonium, and alkylolammonium saltsof higher fatty acids containing from about 8 to about 24 carbon atoms,and preferably from about 12 to about 18 carbon atoms. Soaps can be madeby direct saponification of fats and oils or by the neutralization offree fatty acids. Particularly useful are the sodium and potassium saltsof the mixtures of fatty acids derived from coconut oil and tallow,i.e., sodium or potassium tallow and coconut soap.

If utilized as all or part of the additional particulate material,insoluble organic detergent builders can generally comprise from about2% to 20% by weight of the compositions herein. More preferably, suchbuilder material can comprise from about 4% to 10% by weight of thecomposition.

(d) Inorganic Alkalinity Sources—Another possible type of additionalparticulate material which can be suspended in the liquid detergentcompositions herein can comprise a material which serves to renderaqueous washing solutions formed from such compositions generallyalkaline in nature. Such materials may or may not also act as detergentbuilders, i.e., as materials which counteract the adverse effect ofwater hardness on detergency performance.

Examples of suitable alkalinity sources include water-soluble alkalimetal carbonates, bicarbonates, borates, silicates and metasilicates.Although not preferred for ecological reasons, water-soluble phosphatesalts may also be utilized as alkalinity sources. These include alkalimetal pyrophosphates, orthophosphates, polyphosphates and phosphonates.Of all of these alkalinity sources, alkali metal carbonates such assodium carbonate are the most preferred.

The alkalinity source, if in the form of a hydratable salt, may alsoserve as a desiccant in the liquid detergent compositions herein. Thepresence of an alkalinity source which is also a desiccant may providebenefits in terms of chemically stabilizing those composition componentssuch as the peroxygen bleaching agent which may be susceptible todeactivation by water.

If utilized as all or part of the additional particulate materialcomponent, the alkalinity source will generally comprise from about 1%to 25% by weight of the compositions herein. More preferably, thealkalinity source can comprise from about 2% to 15% by weight of thecomposition. Such materials, while water-soluble, will generally beinsoluble in the non-aqueous detergent compositions described herein.

As indicated hereinafter, the aqueous and non-aqueous liquid detergentcompositions herein may be in the form of bleaching agent and/or othermaterials in particulate form as a solid phase suspended in anddispersed throughout a surfactant-containing, preferably structured,preferably non-aqueous liquid phase. Generally, the structurednon-aqueous liquid phase will comprise from about 49% to 99.95%, morepreferably from about 52% to 98.5%, by weight of the composition withthe dispersed additional solid materials comprising from about 1% to50%, more preferably from about 29% to 44%, by weight of thecomposition.

Very small amounts of water may be incorporated into theparticulate-containing non-aqueous embodiments of the present liquiddetergent composition. However, in such embodiments, the amount of freewater should in no event exceed about 1% by weight of the compositionsherein. More preferably, the water content of the non-aqueous detergentcompositions herein will comprise less than about 1% by weight.

As disclosed herein, the compositions of this invention can also be usedto form aqueous laundry detergent compositions. Additional componentssuitable for use in an aqueous liquid laundry detergent composition canbe found in U.S. Pat. No. 5,783,548, to Fredj et al. and U.S. Pat. No.5,648,327, to Smerznak et al.

The particulate-containing non-aqueous liquid detergent compositionsherein will be relatively viscous and phase stable under conditions ofcommercial marketing and use of such compositions. Frequently theviscosity of the compositions herein will range from about 300 to 8,000cps, more preferably from about 1000 to 4,000 cps. For purposes of thisinvention, viscosity is measured with a Carrimed CSL2 Rheometer at ashear rate of 20 s⁻¹.

The preparation of non-aqueous liquid detergent compositions isdiscussed in detail in Copending application of Jay I. Kahn et al.,entitled “Preparation of Nonaqueous, Particulate-Containing LiquidDetergent Compositions with Surfactant-Structured Liquid Phase”, havingP&G Case No. 6150, Ser. No. 09/202,964, filed on Dec. 23, 1998, now U.S.Pat. No. 6,277,804 which is hereby incorporated by reference.

An effective amount of the liquid detergent compositions herein added towater to form aqueous laundering/bleaching solutions can compriseamounts sufficient to form from about 500 to 10,000 ppm of compositionin aqueous solution. More preferably, from about 800 to 8,000 ppm of thedetergent compositions herein will be provided in aqueouswashing/bleaching solution.

B. Granular/Powder Products

The granular/powder detergent products of the present invention comprisein addition to one or more of the hydrotropes, preferably one or morepreferred ingredients hereinbelow and optionally, one or moreconventional detergent adjunct materials. Such conventional adjunctmaterials can include one or more of the solid particulate materialsdescribed under the Liquid Products section hereinabove or under theConventional Detergent Adjunct Materials section hereinafter.

While the use of hydrotropes is to provide desirable phase formation andproduct viscosity is well-known, the use of these organic molecules ashydrotropes to prevent gelling and/or thickening of the detergentcompositions taught herein and thus improve the dissolution anddispersion performance of a granular detergent product has not beenpreviously disclosed. Gelling has been previously observed in detergentproducts prepared without the hydrotropes as defined in the presentinvention, when the products are first contacted and diluted with water.

Without being limited by theory, it is believed that this gellingphenomenon results from the surfactant-containing particles formingeither viscous surfactant phases (typically lamellar, spherulitic orhexagonal phases) or inner-connected “lump-gels” the upon contact withwater in the wash-liquor or wash-water at certain concentrations ofsurfactant. A correlation has been found between the viscosity of theproduct-water mixture in the critical dilution range where gelling isobserved, and the amount of viscous surfactant phase formed in thisrange.

The problem is particularly pronounced in those areas in which fabriclaundering in automatic clothes washer occurs in relatively cold washwater or under mild agitation (such as in Japan). The typicalsurfactant-water phase diagram shows regions of stability forhigh-viscosity neat or gel surfactant phases at the relatively coldwash-water temperatures. And under conditions of mild agitation, thereis insufficient mechanical energy imparted by the agitator to disruptthe formation of these high-viscosity phases.

The granular detergent compositions taught herein can be either in theform of a single particle or may be in the form of multiple particleseach with its own composition. In the case where the detergent iscomposed of multiple detergent particles, it is preferred that theorganic hydrotrope disclosed above be contained in or coat the surfaceof those particles which are surfactant rich.

Preferred Ingredients

Detersive Surfactants—The anionic surfactants useful in the presentinvention are split into the alkyl sulfate surfactants which accordingto the present invention are separated from the electrolytes in thedetergent composition and the remaining anionic surfactants which may beformulated in either particle. For the purposes of the presentinvention, the alkyl sulfates are defined as alkyl sulfates, alkylalkoxy sulfate, alkyl sulfonates, alkyl alkoxy carboxylate, alkylalkoxylated sulfates with the remaining anionic surfactant beingselected from the group consisting of alkylbenzene sulfonate, alphaolefin sulfonate, paraffin sulfonates, alkyl ester sulfonates,sarcosinates, taurinates, and mixtures thereof.

When present, anionic surfactant will be present typically in aneffective amount in the overall detergent composition. More preferably,the composition may contain at least about 0.5%, more preferably atleast about 5%, even more preferably still, at least about 10% by weightof said composition of anionic surfactant. The composition will alsopreferably contain no more than about 90%, more preferably no more thanabout 50%, even more preferably, no more than about 30% by weight ofsaid composition of anionic surfactant.

Alkyl sulfate surfactants providing excellent overall cleaning abilityalone and particularly when used in combination with polyhydroxy fattyacid amides (see below), including good grease/oil cleaning over a widerange of temperatures, wash concentrations, and wash times, dissolutionof alkyl sulfates can be obtained, as well as improved formulability inliquid detergent formulations are water soluble salts or acids of theformula ROSO3M wherein R preferably is a C10-C24 hydrocarbyl, preferablyan alkyl or hydroxyalkyl having a C10-C20 alkyl component, morepreferably a C12-C18 alkyl or hydroxyalkyl, and M is H or a cation,e.g., an alkali (Group IA) metal cation (e.g., sodium, potassium,lithium), substituted or unsubstituted ammonium cations such as methyl-,dimethyl-, and trimethyl ammonium and quaternary ammonium cations, e.g.,tetramethyl-ammonium and dimethyl piperdinium, and cations derived fromalkanolamines such as ethanolamine, diethanolamine, triethanolamine, andmixtures thereof, and the like. Typically, alkyl chains of C12-16 arepreferred for lower wash temperatures (e.g., below about 50° C.) andC16-18 alkyl chains are preferred for higher wash temperatures (e.g.,above about 50° C.).

Another suitable type of alkyl sulfate surfactant according to thepresent invention are the secondary (2,3) alkyl sulfates. Thesesurfactants preferably are of the formula:

wherein x and (y+1) are integers of at least about 7, preferably atleast about 9. Preferably these surfactants contain from 10 to 18 carbonatoms. Suitable examples of these anionic surfactants are disclosed inU.S. Pat. No. 3,234,258 Morris, issued Feb. 8, 1966; U.S. Pat. No.5,075,041 Lutz, issued Dec. 24, 1991; U.S. Pat. No. 5,349,101 Lutz etal., issued Sep. 20, 1994; and U.S. Pat. No. 5,389,277 Prieto, issuedFeb. 14, 1995 each incorporated herein by reference.

Another suitable type of alkyl sulfate surfactant according to thepresent invention are the alkyl alkoxylated sulfate. These surfactantsare water soluble salts or acids typically of the formula RO(A)mSO3Mwherein R is an unsubstituted C10-C24 alkyl or hydroxyalkyl group havinga C10-C24 alkyl component, preferably a C12-C20 alkyl or hydroxyalkyl,more preferably C12-C18 alkyl or hydroxyalkyl, A is an ethoxy or propoxyunit, m is greater than zero, typically between about 0.5 and about 6,more preferably between about 0.5 and about 3, and M is H or a cationwhich can be, for example, a metal cation (e.g., sodium, potassium,lithium, etc.), ammonium or substituted-ammonium cation. Alkylethoxylated sulfates as well as alkyl propoxylated sulfates arecontemplated herein. Specific examples of substituted ammonium cationsinclude methyl-, dimethyl-, trimethyl-ammonium and quaternary ammoniumcations, such as tetramethyl-ammonium, dimethyl piperidinium and cationsderived from alkanolamines, e.g. monoethanolamine, diethanolamine, andtriethanolamine, and mixtures thereof. Exemplary surfactants are C12-C18alkyl polyethoxylate (1.0) sulfate, C12-C18 alkyl polyethoxylate (2.25)sulfate, C12-C18 alkyl polyethoxylate (3.0) sulfate, and C12-C18 alkylpolyethoxylate (4.0) sulfate wherein M is conveniently selected fromsodium and potassium. Surfactants for use herein can be made fromnatural or synthetic alcohol feedstocks. Chain lengths represent averagehydrocarbon distributions, including branching. The anionic surfactantcomponent may comprise alkyl sulfates and alkyl ether sulfates derivedfrom conventional alcohol sources, e.g., natural alcohols, syntheticalcohols such as those sold under the trade name of NEODOL™, ALFOL™,LIALL™, LUTENSOL™ and the like. Alkyl ether sulfates are also known asalkyl polyethoxylate sulfates.

Another type of alkyl sulfate surfactant according to the presentinvention are one or more (preferably a mixture of two or more)mid-chain branched surfactants, preferably mid-chain branched alkylalkoxy alcohols having the formula:

mid-chain branched alkyl sulfates having the formula:

and mid-chain branched alkyl alkoxy sulfates having the formula:

wherein the total number of carbon atoms in the branched primary alkylmoiety of these formulae (including the R, R¹, and R² branching, but notincluding the carbon atoms which comprise any EO/PO alkoxy moiety) isfrom 14 to 20, and wherein further for this surfactant mixture theaverage total number of carbon atoms in the branched primary alkylmoieties having the above formula is within the range of greater than14.5 to about 17.5 (preferably from about 15 to about 17); R, R¹, and R²are each independently selected from hydrogen, C₁-C₃ alkyl, and mixturesthereof, preferably methyl; provided R, R¹, and R² are not all hydrogenand, when z is 1, at least R or R¹ is not hydrogen. M is a water solublecation and may comprises more than one type of cation, for example, amixture of sodium and potassium. The index w is an integer from 0 to 13;x is an integer from 0 to 13; y is an integer from 0 to 13; z is aninteger of at least 1; provided w+x+y+z is from 8 to 14. EO and POrepresent ethylencoxy units and propyleneoxy units having the formula:

respectively, however, other alkoxy units inter alia 1,3-propyleneoxy,butoxy, and mixtures thereof are suitable as alkoxy units appended tothe mid-chain branched alkyl moieties.

The mid-chain branched surfactants are preferably mixtures whichcomprise a surfactant system. Therefore, when the surfactant systemcomprises an alkoxylated surfactant, the index m indicates the averagedegree of alkoxylation within the mixture of surfactants. As such, theindex m is at least about 0.01, preferably within the range of fromabout 0.1, more preferably from about 0.5, most preferably from about 1to about 30, preferably to about 10, more preferably to about 5. Whenconsidering a mid-chain branched surfactant system which comprises onlyalkoxylated surfactants, the value of the index m represents adistribution of the average degree of alkoxylation corresponding to m,or it may be a single specific chain with alkoxylation (e.g.,ethoxylation and/or propoxylation) of exactly the number of unitscorresponding to m.

The preferred mid-chain branched surfactants of the present inventionwhich are suitable for use in the surfactant systems of the presentinvention have the formula:

wherein a, b, d, and e are integers such that a+b is from 10 to 16 andd+e is from 8 to 14; M is selected from sodium, potassium, magnesium,ammonium and substituted ammonium, and mixtures thereof.

The surfactant systems of the present invention which comprise mid-chainbranched surfactants are preferably formulated in two embodiments. Afirst preferred embodiment comprises mid-chain branched surfactantswhich are formed from a feedstock which comprises 25% or less ofmid-chain branched alkyl units. Therefore, prior to admixture with anyother conventional surfactants, the mid-chain branched surfactantcomponent will comprise 25% or less of surfactant molecules which arenon-linear surfactants.

A second preferred embodiment comprises mid-chain branched surfactantswhich are formed from a feedstock which comprises from about 25% toabout 70% of mid-chain branched alkyl units. Therefore, prior toadmixture with any other conventional surfactants, the mid-chainbranched surfactant component will comprise from about 25% to about 70%surfactant molecules which are non-linear surfactants.

These surfactants are further described in U.S. Patent Application No.60/061,971, Oct. 14, 1997, No. 60/061,975, Oct. 14, 1997, No.60/062,086, Oct. 14, 1997, No. 60/061,916, Oct. 14, 1997, No.60/061,970, Oct. 14, 1997, No. 60/062,407, Oct. 14, 1997. Other suitablemid-chain branched surfactants can be found in U.S. Patent applicationSer. Nos. 60/032,035, 60/031,845, 60/031,916, 60/031,917, 60/031,761,60/031,762, and 60/031,844. Mixtures of these branched surfactants withconventional linear surfactants are also suitable for use in the presentcompositions.

Of the anionic surfactants according to the present invention which arenot included in the alkyl sulfates according to the present inventionone type of anionic surfactant which can be utilized encompasses alkylester sulfonates. These are desirable because they can be made withrenewable, non-petroleum resources. Preparation of the alkyl estersulfonate surfactant component can be effected according to knownmethods disclosed in the technical literature. For instance, linearesters of C8-C20 carboxylic acids can be sulfonated with gaseous SO3according to “The Journal of the American Oil Chemists Society,” 52(1975), pp. 323-329. Suitable starting materials would include naturalfatty substances as derived from tallow, palm, and coconut oils, etc.

The preferred alkyl ester sulfonate surfactant, especially for laundryapplications, comprises alkyl ester sulfonate surfactants of thestructural formula:

wherein R3 is a C8-C20 hydrocarbyl, preferably an alkyl, or combinationthereof, R4 is a C1-C6 hydrocarbyl, preferably an alkyl, or combinationthereof, and M is a soluble salt-forming cation. Suitable salts includemetal salts such as sodium, potassium, and lithium salts, andsubstituted or unsubstituted ammonium salts, such as methyl-, dimethyl,-trimethyl, and quaternary ammonium cations, e.g. tetramethyl-ammoniumand dimethyl piperdinium, and cations derived from alkanolamines, e.g.monoethanol-amine, diethanolamine, and triethanolamine. Preferably, R3is C10-C16 alkyl, and R4 is methyl, ethyl or isopropyl. Especiallypreferred are the methyl ester sulfonates wherein R3 is C14-C16 alkyl.

Another type of anionic surfactant which can be utilized encompassesalkylbenzenesulphonates. These include the hard (ABS, TPBS), lineartypes, also known as LAS, and made by known process such as various HFor solid HF e.g., DETAL® (UOP) process, or made by using other LewisAcid catalysts e.g., AlCl₃, or made using acidic silica/alumina or madefrom chlorinated hydrocarbons, such as C₉-C₂₀ linear alkylbenzenesulfonates, particularly sodium linear alkyl C₁₀-C₁₅ benzene sulfonate.These surfactants are water soluble salts or acids typically of theformula RASO3M wherein R is a branched or linear C10-C24 alkyl group,preferably a C10-C20 alkyl, more preferably C10-C18 alkyl, A is an arylgroup, preferably benzene, or toluene, more preferably benzene unit, andM is H or a cation which can be, for example, a metal cation (e.g.,sodium, potassium, lithium, etc.), ammonium or substituted-ammoniumcation.

The surfactant systems of the laundry detergent compositions of thepresent invention can also comprise from about 0.001%, preferably fromabout 1%, more preferably from about 5%, most preferably from about 10%to about 100%, preferably to about 60%, more preferably to about 30% byweight, of the surfactant system, of one or more (preferably a mixtureof two or more) modified alkyl arylsulfonate surfactants, or MLASpreferably surfactants wherein the aryl unit is a benzene ring havingthe formula:

wherein L is an acyclic hydrocarbyl moiety comprising from 6 to 18carbon atoms; R¹, R², and R³ are each independently hydrogen or C₁-₃alkyl, provided R¹ and R² are not attached at the terminus of the Lunit; M is a water soluble cation having charge q wherein a and b aretaken together to satisfy charge neutrality.

These and other suitable MLAS surfactants are further described incopending U.S. Patent Applications No. 60/053,319 filed on Jul. 21,1997, No. 60/053,318, filed on Jul. 21, 1997, No. 60/053,321, filed onJul. 21, 1997, No. 60/053,209, filed on Jul. 21, 1997, No. 60/053,328,filed on Jul. 21, 1997, No. 60/053,186, filed on Jul. 21, 1997, No.60/105,017 filed on Oct. 20, 1998, No. 60/104,962 filed on Oct. 20,1998, and No. 60/144,519 filed on Jul. 19, 1999. Mixtures of thesemodified surfactants with conventional surfactants and/or branchedsurfactants, such as those described herein, are also suitable for usein the present compositions.

Examples of suitable anionic surfactants are given in “Surface ActiveAgents and Detergents” (Vol. I and II by Schwartz, Perry and Berch). Avariety of such surfactants are also generally disclosed in U.S. Pat.No. 3,929,678, issued Dec. 30, 1975 to Laughlin, et al. at Column 23,line 58 through Column 29, line 23.

Other anionic surfactants useful for detersive purposes can also beincluded in the compositions hereof. These can include salts (including,for example, sodium, potassium, ammonium, and substituted ammonium saltssuch as mono-, di- and triethanolamine salts) of soap, C8-C22 primary orsecondary alkanesulphonates, C8-C24 olefinsulphonates, sulphonatedpolycarboxylic acids prepared by sulphonation of the pyrolyzed productof alkaline earth metal citrates, e.g., as described in British patentspecification No. 1,082,179, alkyl glycerol sulfonates, fatty acylglycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenolethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates,isothionates such as the acyl isothionates, N-acyl taurates, fatty acidamides of methyl tauride, alkyl succinamates and sulfosuccinates,monoesters of sulfosuccinate (especially saturated and unsaturatedC12-C18 monoesters) diesters of sulfosuccinate (especially saturated andunsaturated C6-C14 diesters), N-acyl sarcosinates, sulfates ofalkylpolysaccharides such as the sulfates of alkylpolyglucoside (thenonionic nonsulfated compounds being described below), branched primaryalkyl sulfates, alkyl polyethoxy carboxylates such as those of theformula RO(CH2CH2O)kCH2COO—M+wherein R is a C8-C22 alkyl, k is aninteger from 0 to 10, and M is a soluble salt-forming cation, and fattyacids esterified with isethionic acid and neutralized with sodiumhydroxide. Resin acids and hydrogenated resin acids are also suitable,such as rosin, hydrogenated rosin, and resin acids and hydrogenatedresin acids present in or derived from tall oil. Further examples aregiven in “Surface Active Agents and Detergents” (Vol. I and II bySchwartz, Perry and Berch). A variety of such surfactants are alsogenerally disclosed in U.S. Pat. No. 3,929,678, issued Dec. 30, 1975 toLaughlin, et al. at Column 23, line 58 through Column 29, line 23.

Another type of useful anionic surfactant are the so-called dianionics.These are surfactants which have at least two anionic groups present onthe surfactant molecule. Some suitable dianionic surfactants are furtherdescribed in copending U.S. Ser. Nos. 60/020,503, 60/020,772,60/020,928, 60/020,832 and 60/020,773 all filed on Jun. 28, 1996, and60/023,539, 60/023,493, 60/023,540 and 60/023,527 filed on Aug. 8, 1996,the disclosures of which are incorporated herein by reference.

C. Tablet Products

The tablet detergent products of the present invention comprise inaddition to one or more of the hydrotropes (“binding agents” becausethey have a cohesive effect on the tablets), preferably one or morepreferred ingredients hereinbelow and optionally, one or moreconventional detergent adjunct materials. Such conventional adjunctmaterials can include one or more of the solid particulate materialsdescribed under the Liquid Products section and/or Granular/PowderProducts section hereinabove or under the Conventional Detergent AdjunctMaterials section hereinafter.

Detergent tablet formulations generally contain at least a small amountof binding agent in the composition in order to provide a cohesiveeffect and promote the integrity of the tablets. For the purpose of thisinvention, the Cohesive Effect on the particulate material of adetergent matrix is characterised by the force required to break atablet based on the examined detergent matrix pressed under controlledcompression conditions. Means to assess tablet strength (also refer todiametrical fracture stress) are given in Pharmaceutical dosage forms:tablets volume 1 Ed. H. A. Lieberman et al, published in 1989.

It has been found that the addition of these hydrotrope compounds to aparticulate material prepared according to the present invention has acohesive effect while also providing excellent disintegrationperformance in wash-water when it is formed into a tablet by compressingthe particulate material. Detergent tablets containing this hydrotropehave a higher tensile strength at constant compacting force or an equaltensile strength at lower compacting force when compared to traditionaltablets.

In addition to the cohesive effect that they provide, these hydrotropesalso provide the key ingredient to prevent gelling and/or thickening ofthe detergent compositions taught herein. Gelling has been previouslyobserved in detergent products prepared without the hydrotropes asdefined in the present invention, when the products are first contactedand diluted with water. Without being limited by theory, it is believedthat this gelling phenomenon results from the surfactant-containingparticles forming viscous surfactant phases (typically lamellar,spherulitic or hexagonal phases) upon contact with water in thewash-liquor or wash-water at certain concentrations of surfactant. Acorrelation has been found between the viscosity of the product-watermixture in the critical dilution range where gelling is observed, andthe amount of viscous surfactant phase formed in this range.

Without being bound by theory, it is believed that the hydrotropesdescribed above prevent the formation of the viscous surfactant phasesformed upon dilution, because the hydrotrope can effectively interactwith the ordered, structured layers of surfactant molecules, disruptthem and promote the formation of isotropic low-viscosity surfactantphases.

In the present invention, there is also an additional benefit that theinclusion of these special hydrotropes expands the “operating window” ofthe detergent tablets. The operating window relates to the range in thebulk density of the detergent tablets, when the detergent tablets aremanufactured on an industrial scale. Because of several variables,during the industrial-scale manufacture of detergent tablets the densityof the detergent tablets varies somewhat from the ideal or preferreddensity. The operating window is the range of densities surrounding thepreferred density where the tablet is not at the preferred density butis still acceptable. Below the operating window, the density is too lowas a result of insufficient packing and cohesion during the compressionstep and thus the tablet is very friable and likely to be broken duringhandling and storage. Above the operating window, the tablet is packedtoo tightly and is likely to be insufficiently dissolved and dispersedin a wash liquor during a wash process.

In addition to these hydrotropes discussed above, the present detergenttablets may also include additional non-gelling binders. Non-gellingbinders not only provide cohesive benefits, but also facilitatedissolution.

If non gelling binders are used, suitable non-gelling binders includesynthetic organic polymers such as polyethylene glycols,polyvinylpyrrolidones, polyacrylates and water-soluble acrylatecopolymers. The handbook of Pharmaceutical Excipients second edition,has the following binders classification: Acacia, Alginic Acid,Carbomer, Carboxymethylcellulose sodium, Dextrin, Ethylcellulose,Gelatin, Guar gum, Hydrogenated vegetable oil type I, Hydroxyethylcellulose, Hydroxypropyl methylcellulose, Liquid glucose, Magnesiumaluminum silicate, Maltodextrin, Methylcellulose, polymethacrylates,povidone, sodium alginate, starch and zein. Most preferable binders alsohave an active cleaning function in the laundry wash such as cationicpolymers, i.e. ethoxylated hexamethylene diamine quaternary compounds,bishexamethylene triamines, or others such as pentaamines, ethoxylatedpolyethylene amines, maleic acrylic polymers.

Non-gelling binder materials are preferably sprayed on and hence have anappropriate melting point temperature below 90° C., preferably below 70°C. and even more preferably below 50° C. so as not to damage or degradethe other active ingredients in the matrix. Most preferred arenon-aqueous liquid binders (i.e. not in aqueous solution) which may besprayed in molten form. However, they may also be solid bindersincorporated into the matrix by dry addition but which have bindingproperties within the tablet.

The detergent tablets prepared according to the present invention willcomprise from about 0.05% to about 5%, preferably from about 0.1% toabout 3%, most preferably from about 0.1% to about 1% of the essentialhydrotrope in which two polar groups are separated from each other by atleast 5, preferably 6, aliphatic carbon atoms. When the optionalnon-gelling binder materials are used, they will be present in thedetergent tablets, they will be used in levels of from about 0.1% toabout 7%, pref. from about 0.5% to about 5%, more pref. from about 1% toabout 3% of the detergent tablet. When the optional non-gelling bindersare used they will be present in the detergent tablets in a ratio ofnon-gelling binder to special hydrotrope binder of from about 2:1 toabout 60:1, preferably from about 3:1 to about 30:1, more preferablyfrom about 3:1 to about 15:1.

Disintegrants—Although it is necessary that the tablets should have goodintegrity before use, it is necessary also that they should disintegraterapidly during use, when contacted with wash-water. Thus it is alsoknown to include a disintegrant which will promote disintegration of thetablet. Various classes of disintegrant are known, including the classin which disintegration is caused by swelling of the disintegrant.Various swelling disintegrants have been proposed in the literature,with the preference being directed predominantly towards starches,celluloses and water soluble organic polymers. Inorganic swellingdisintegrants such as bentonite clay have also been mentioned, forinstance in EP-A-466,484.

Some materials acts as binder and disintegrant. It is also mentionedtherein that the disintegrant may give supplementary building,anti-redeposition or fabric softening properties. The amount ofdisintegrant is preferably 1 to 5%. It is proposed in EP-A-466,484 thatthe tablet may have a heterogeneous structure comprising a plurality ofdiscrete regions, for example layers, inserts or coatings.

Tablet Manufacture—Detergent tablets of the present invention can beprepared simply by mixing the solid ingredients together and compressingthe mixture in a conventional tablet press as used, for example, in thepharmaceutical industry. Preferably the principal ingredients, inparticular gelling surfactants, are used in particulate form. Any liquidingredients, for example surfactant or suds suppressor, can beincorporated in a conventional manner into the solid particulateingredients.

The ingredients such as builder and surfactant can be spray-dried in aconventional manner and then compacted at a suitable pressure.Preferably, the tablets according to the invention are compressed usinga force of less than 100000N, more preferably of less than 50000N, evenmore preferably of less than 5000N and most preferably of less than 3000N. Indeed, the most preferred embodiment is a tablet compressed using aforce of less than 2500N.

The particulate material used for making the tablet of this inventioncan be made by any particulation or granulation process. An example ofsuch a process is spray drying (in a co-current or counter current spraydrying tower) which typically gives low bulk densities 600 g/l or lower.Particulate materials of higher density can be prepared by granulationand densification in a high shear batch mixer/granulator or by acontinuous granulation and densification process (e.g. using Lodige(R)CB and/or Lodige(R) KM mixers). Other suitable processes include fluidbed processes, compaction processes (e.g. roll compaction), extrusion,as well as any particulate material made by any chemical process likeflocculation, crystallisation sentering, etc. Individual particles canalso be any other particle, granule, sphere or grain.

The components of the particulate material may be mixed together by anyconventional means. Batch is suitable in, for example, a concrete mixer,Nauta mixer, ribbon mixer or any other. Alternatively the mixing processmay be carried out continuously by metering each component by weight onto a moving belt, and blending them in one or more drum(s) or mixer(s).Non-gelling binder can be sprayed on to the mix of some, or all of, thecomponents of the particulate material. Other liquid ingredients mayalso be sprayed on to the mix of components either separately orpremixed. For example perfume and slurries of optical brighteners may besprayed. A finely divided flow aid (dusting agent such as zeolites,carbonates, silicas) can be added to the particulate material afterspraying the binder, preferably towards the end of the process, to makethe mix less sticky.

The tablets may be manufactured by using any compacting process, such astabletting, briquetting, or extrusion, preferably tabletting. Suitableequipment includes a standard single stroke or a rotary press (such asCourtoy(R), Korch(R), Manesty(R), or Bonals(R)). The tablets preparedaccording to this invention preferably have a diameter of between 20 mmand 60 mm, preferably of at least 35 and up to 55 mm, and a weightbetween 15 g and 100 g. The ratio of height to diameter (or width) ofthe tablets is preferably greater than 1:3, more preferably greater than1:2. The compaction pressure used for preparing these tablets need notexceed 100000 kN/m2, preferably not exceed 30000 kN/m2, more preferablynot exceed 5000 kN/m2, even more preferably not exceed 3000 kN/m2 andmost preferably not exceed 1000 kN/m2. In a preferred embodimentaccording to the invention, the tablet has a density of at least 0.9g/cc, more preferably of at least 1.0 g/cc, and preferably of less than2.0 g/cc, more preferably of less than 1.5 g/cc, even more preferably ofless than 1.25 g/cc and most preferably of less than 1.1 g/cc.

Multi-layer tablets can be made by known techniques.

Coating—Solidity of the tablet according to the invention may be furtherimproved by making a coated tablet, the coating covering a non-coatedtablet according to the invention, thereby further improving themechanical characteristics of the tablet while maintaining or furtherimproving dispersion.

In one embodiment of the present invention, the tablets may then becoated so that the tablet does not absorb moisture, or absorbs moistureat only a very slow rate. The coating is also strong so that moderatemechanical shocks to which the tablets are subjected during handling,packing and shipping result in no more than very low levels of breakageor attrition. Finally the coating is preferably brittle so that thetablet breaks up when subjected to stronger mechanical shock.Furthermore it is advantageous if the coating material is dispersedunder alkaline conditions, or is readily emulsified by surfactants. Thiscontributes to avoiding the problem of visible residue in the window ofa front-loading washing machine during the wash cycle, and also avoidsdeposition of particles or lumps of coating material on the laundryload.

Water solubility is measured following the test protocol of ASTME1148-87 entitled, “Standard Test Method for Measurements of AqueousSolubility”.

Suitable coating materials are dicarboxylic acids. Particularly suitabledicarboxylic acids are selected from the group consisting of oxalicacid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelicacid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid,dodecanedioic acid, tridecanedioic acid and mixtures thereof. Thecoating material has a melting point preferably of from 40° C. to 200°C.

The coating can be applied in a number of ways. Two preferred coatingmethods are a) coating with a molten material and b) coating with asolution of the material.

In a), the coating material is applied at a temperature above itsmelting point, and solidifies on the tablet. In b), the coating isapplied as a solution, the solvent being dried to leave a coherentcoating. The substantially insoluble material can be applied to thetablet by, for example, spraying or dipping. Normally when the moltenmaterial is sprayed on to the tablet, it will rapidly solidify to form acoherent coating. When tablets are dipped into the molten material andthen removed, the rapid cooling again causes rapid solidification of thecoating material. Clearly substantially insoluble materials having amelting point below 40° C. are not sufficiently solid at ambienttemperatures and it has been found that materials having a melting pointabove about 200° C. are not practicable to use. Preferably, thematerials melt in the range from 60° C. to 160° C., more preferably from70° C. to 120° C.

By “melting point” is meant the temperature at which the material whenheated slowly in, for example, a capillary tube becomes a clear liquid.

A coating of any desired thickness can be applied according to thepresent invention. For most purposes, the coating forms from 1% to 10%,preferably from 1.5% to 5%, of the tablet weight.

The tablet coatings are preferably very hard and provide extra strengthto the tablet.

In a preferred embodiment of the present invention the fracture of thecoating in the wash is improved by adding a disintegrant in the coating.This disintegrant will swell once in contact with water and break thecoating in small pieces. This will improve the dispersion of the coatingin the wash solution. The disintegrant is suspended in the coating meltat a level of up to 30%, preferably between 5% and 20%, most preferablybetween 5 and 10% by weight. Possible disintegrants are described inHandbook of Pharmaceutical Excipients (1986). Examples of suitabledisintegrants include starch: natural, modified or pregelatinizedstarch, sodium starch gluconate; gum: agar gum, guar gum, locust beangum, karaya gum, pectin gum, tragacanth gum; croscarmylose Sodium,crospovidone, cellulose, carboxymethyl cellulose, algenic acid and itssalts including sodium alginate, silicone dioxide, clay,polyvinylpyrrolidone, soy polysacharides, ion exchange resins andmixtures thereof.

Tensile Strength—Depending on the composition of the starting material,and the shape of the tablets, the used compacting force may be adjustedto not affect the tensile strength, and the disintegration time in thewashing machine. This process may be used to prepare homogenous orlayered tablets of any size or shape.

For a cylindrical tablet, the tensile strength corresponds to thediametrical fracture stress (DFS) which is a way to express the strengthof a tablet, and is determined by the following equation:$= \frac{2F}{\pi\quad D\quad t}$

Where F is the maximum force (Newton) to cause tensile failure(fracture) measured by a VK 200 tablet hardness tester supplied by VanKell industries, Inc. D is the diameter of the tablet, and t thethickness of the tablet.

(Method Pharmaceutical Dosage Forms Tablets Volume 2 Page 213 to 217). Adiametral fracture stress of at least 25 kPa is preferred.

This applies similarly to non cylindrical tablets, to define the tensilestrength, whereby the cross section normal to the height of the tabletis non round, and whereby the force is applied along a directionperpendicular to the direction of the height of the tablet and normal tothe side of the tablet, the side being perpendicular to the non roundcross section.

Optional Conventional Detergent Adjunct Ingredients

In addition to the components of the compositions of the presentinvention hereinabove described, the detergent compositions herein can,and preferably will, contain various other optional components.

(a) Inorganic Detergent Builders—The detergent compositions herein mayalso optionally contain one or more types of inorganic detergentbuilders beyond those listed hereinbefore that also function asalkalinity sources. Such optional inorganic builders can include, forexample, aluminosilicates such as zeolites. Aluminosilicate zeolites,and their use as detergent builders are more fully discussed in Corkillet al., U.S. Pat. No. 4,605,509; Issued Aug. 12, 1986, the disclosure ofwhich is incorporated herein by reference. Also crystalline layeredsilicates, such as those discussed in this '509 U.S. patent, are alsosuitable for use in the detergent compositions herein. If utilized,optional inorganic detergent builders can comprise from about 2% to 15%by weight of the compositions herein.(b) Enzymes—Enzymes can be included in the formulations herein for awide variety of fabric laundering purposes, including removal ofprotein-based, carbohydrate-based, or triglyceride-based stains; for theprevention of refugee dye transfer; and for fabric restoration. It isbelieved that the addition of the special hydrotropes described abovewill enhance the performance of enzymes in a detergent composition. Thisis because as the hydrotropes increase the rate of dissolution of thedetergent composition, the rate at which enzymes come into contact withwater and are activated will also increase and the correspondingdetersive benefits provided by activated enzymes will also increase.This behavior is seen in both aqueous and non-aqueous detergentcompositions.

The enzymes to be incorporated include proteases, amylases, lipases,mannanase, cellulases, and peroxidases, as well as mixtures thereof.Other types of enzymes may also be included. They may be of any suitableorigin, such as vegetable, animal, bacterial, fungal and yeast origin.However, their choice is governed by several factors such as pH-activityand/or stability optima, thermostability, stability versus activedetergents, builders and so on. In this respect bacterial or fungalenzymes are preferred, such as bacterial amylases and proteases, andfungal cellulases.

Enzymes are normally incorporated at levels sufficient to provide up toabout 5 mg by weight, more typically about 0.01 mg to about 3 mg, ofactive enzyme per gram of the composition. Stated otherwise, thecompositions herein will typically comprise from about 0.001% to about5%, preferably 0.01%-1.0% by weight of a commercial enzyme preparation.Protease enzymes are usually present in such commercial preparations atlevels sufficient to provide from 0.005 to 0.1 Anson units (AU) ofactivity per gram of composition.

Suitable examples of proteases are the subtilisins which are obtainedfrom particular strains of Bacillus subtilis and Bacillus licheniforms.Another suitable protease is obtained from a strain of Bacillus, havingmaximum activity throughout the pH range of 8-12, developed and sold byNovo Industries A/S under the registered trade name ESPERASE®. Thepreparation of this enzyme and analogous enzymes is described in BritishPatent Specification No. 1,243,784 of Novo Industries A/S. Proteolyticenzymes suitable for removing protein-based stains that are commerciallyavailable include those sold under the tradenames ALCALASE® andSAVINASE® by Novo Industries A/S (Denmark) and MAXATASE® byInternational Bio-Synthetics, Inc. (The Netherlands). Other proteasesinclude Protease A (see European Patent Application 130,756, publishedJan. 9, 1985) and Protease B (see European Patent Application Serial No.87303761.8, filed Apr. 28, 1987, and European Patent Application130,756, Bott et al., published Jan. 9, 1985).

Amylases include, for example, amylases described in British PatentSpecification No. 1,296,839 (Novo Industries A/S), RAPIDASE®,International Bio-Synthetics, Inc. and TERMAMYL®, Novo Industries A/S.

Mannanases include the following three mannans-degrading enzymes: EC3.2.1.25: β*mannosidase, EC 3.2.1.78: Endo-1,4-β-mannosidase, referredtherein after as “mannanase” and EC 3.2.1.100: 1,4-β-mannobiosidase(IUPAC Classification—Enzyme nomenclature, 1992 ISBN 0-12-227165-3Academic Press).

More preferably, the detergent compositions of the present inventioncomprise a β-1,4-Mannosidase (E.C. 3.2.1.78) referred to as Mannanase.The term “mannanase” or “galactomannanase” denotes a mannanase enzymedefined according to the art as officially being named mannanendo-1,4-beta-mannosidase and having the alternative namesbeta-mannanase and endo-1,4-mannanase and catalysing the reaction:random hydrolysis of 1,4-beta-D-mannosidic linkages in mannans,galactomannans, glucomannans, and galactoglucomannans. In particular,Mannanases (EC 3.2.1.78) constitute a group of polysaccharases whichdegrade mannans and denote enzymes which are capable of cleaving polyosechains containing mannose units, i.e. are capable of cleaving glycosidicbonds in mannans, glucomannans, galactomannans and galactogluco-mannans.Mannans are polysaccharides having a backbone composed of β-1,4-linkedmannose; glucomannans are polysaccharides having a backbone or more orless regularly alternating β-1,4 linked mannose and glucose;galactomannans and galactoglucomannans are mannans and glucomannans withα-1,6 linked galactose sidebranches. These compounds may be acetylated.

The cellulase enzymes used in the instant detergent composition arepreferably incorporated at levels sufficient to provide up to about 5 mgby weight, more preferably about 0.01 mg to about 3 mg, of active enzymeper gram of the composition. Stated otherwise, the compositions hereinpreferably comprise from about 0.001% to about 5%, preferably 0.01%-1.0%by weight of a commercial enzyme preparation. The cellulase usable inthe present invention includes both bacterial or fungal cellulase.Preferably, they will have a pH optimum of between 5 and 9.5. Suitablecellulases are disclosed in U.S. Pat. No. 4,435,307, Barbesgoard et al,issued Mar. 6, 1984, which discloses fungal cellulase produced fromHumicola insolens and Humicola strain DSM 1800 or a cellulase212-producing microorganism belonging to the genus Aeromonas, andcellulase extracted from the hepatopancreas of a marine mollusk(Dolabella Auricula Solander). Suitable cellulases are also disclosed inGB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832. In addition,cellulase especially suitable for use herein are disclosed in WO92-13057 (The Procter & Gamble Company). Most preferably, the cellulasesused in the instant detergent compositions are purchased commerciallyfrom NOVO Industries A/S under the product names CAREZYME® andCELLUZYME®.

Suitable lipase enzymes for detergent usage include those produced bymicroorganisms of the Pseudomonas group, such as Pseudomonas stutzeriATCC 19.154, as disclosed in British Patent 1,372,034. See also lipasesin Japanese Patent Application 53,20487, laid open to public inspectionon Feb. 24, 1978. This lipase is available from Amano Pharmaceutical Co.Ltd., Nagoya, Japan, under the trade name Lipase P AMANO®, hereinafterreferred to as “Amano-P.” Other commercial lipases include AMANO-CES®,lipases from Chromobacter viscosum, e.g. Chromobacter viscosum var.lipolyticum NRRLB 3673, commercially available from Toyo Jozo Co.,Tagata, Japan; and further Chromobacter viscosum lipases from U.S.Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and lipasesfrom Pseudomonas gladioli. The LIPOLASE® enzyme derived from Humicolalanuginosa and commercially available from Novo Industries A/S(see alsoEPO 341,947) is a preferred lipase for use herein.

Peroxidase enzymes are used in combination with oxygen sources, e.g.,percarbonate, perborate, persulfate, hydrogen peroxide, etc. They areused for “solution bleaching,” i.e. to prevent transfer of dyes orpigments removed from substrates during wash operations to othersubstrates in the wash solution. Peroxidase enzymes are known in theart, and include, for example, horseradish peroxidase, ligninase, andhaloperoxidase such as chloro- and bromo-peroxidase.Peroxidase-containing detergent compositions are disclosed, for example,in PCT International Application WO 89/099813, published Oct. 19, 1989,by O. Kirk, assigned to Novo Industries A/S.

A wide range of enzyme materials and means for their incorporation intosynthetic detergent compositions are also disclosed in U.S. Pat. No.3,553,139, issued Jan. 5, 1971 to McCarty et al. Enzymes are furtherdisclosed in U.S. Pat. No. 4,101,457, Place et al, issued Jul. 18, 1978,and in U.S. Pat. No. 4,507,219, Hughes, issued Mar. 26, 1985. Enzymematerials useful for liquid detergent formulations, and theirincorporation into such formulations, are disclosed in U.S. Pat. No.4,261,868, Hora et al, issued Apr. 14, 1981. Enzymes for use indetergents can be stabilized by various techniques. Enzyme stabilizationtechniques are disclosed and exemplified in U.S. Pat. No. 3,600,319,issued Aug. 17, 1971 to Gedge, et al., and European Patent ApplicationPublication No. 0 199 405, Application No. 86200586.5, published Oct.29, 1986, Venegas. Enzyme stabilization systems are also described, forexample, in U.S. Pat. No. 3,519,570. Enzymes added to the compositionsherein in the form of conventional enzyme prills are especiallypreferred for use herein. Such prills will generally range in size fromabout 100 to 1,000 microns, more preferably from about 200 to 800microns and will be suspended throughout the liquid phase of thecomposition. Prills in the compositions of the present invention havebeen found, in comparison with other enzyme forms, to exhibit especiallydesirable enzyme stability in terms of retention of enzymatic activityover time. Thus, compositions which utilize enzyme prills need notcontain conventional enzyme stabilizing such as must frequently be usedwhen enzymes are incorporated into aqueous liquid detergents.

(c) Chelating Agents—The detergent compositions herein may alsooptionally contain a chelating agent which serves to chelate metal ions,e.g., iron and/or manganese, within the detergent compositions herein.Such chelating agents thus serve to form complexes with metal impuritiesin the composition which would otherwise tend to deactivate compositioncomponents such as the peroxygen bleaching agent. Useful chelatingagents can include amino carboxylates, phosphonates, amino phosphonates,polyfunctionally-substituted aromatic chelating agents and mixturesthereof.

Amino carboxylates useful as optional chelating agents includeethylenediaminetetraacetates, N-hydroxyethyl-ethylenediaminetriacetates,nitrilotriacetates, ethylene-diamine tetrapropionates,triethylenetetraaminehexacetates, diethylenetriaminepentaacetates,ethylenediaminedisuccinates and ethanol diglycines. The alkali metalsalts of these materials are preferred.

Amino phosphonates are also suitable for use as chelating agents in thecompositions of this invention when at least low levels of totalphosphorus are permitted in detergent compositions, and includeethylenediaminetetrakis (methylene-phosphonates) as DEQUEST. Preferably,these amino phosphonates do not contain alkyl or alkenyl groups withmore than about 6 carbon atoms.

Preferred chelating agents include hydroxy-ethyldiphosphonic acid(HEDP), diethylene triamine penta acetic acid (DTPA), ethylenediaminedisuccinic acid (EDDS) and dipicolinic acid (DPA) and salts thereof. Thechelating agent may, of course, also act as a detergent builder duringuse of the compositions herein for fabric laundering/bleaching. Thechelating agent, if employed, can comprise from about 0.1% to 4% byweight of the compositions herein. More preferably, the chelating agentwill comprise from about 0.2% to 2% by weight of the detergentcompositions herein.

(d) Suds Suppressors—Suds suppression can be of particular importance inthe present invention because of the high concentration of the detergentcomposition. The use of suds suppressors in “high concentration cleaningprocess” is described in greater detail U.S. Pat. Nos. 4,489,455 and4,489,574.

A wide variety of materials may be used as suds suppressors, and sudssuppressors are well known to those skilled in the art. See, forexample, Kirk Othmer Encyclopedia of Chemical Technology, Third Edition,Volume 7, pages 430-447 (John Wiley & Sons, Inc., 1979). One category ofsuds suppressor of particular interest encompasses monocarboxylic fattyacid and soluble salts therein. See U.S. Pat. No. 2,954,347, issued Sep.27, 1960 to Wayne St. John. The monocarboxylic fatty acids and saltsthereof used as suds suppressor typically have hydrocarbyl chains of 10to about 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitablesalts include the alkali metal salts such as sodium, potassium, andlithium salts, and ammonium and alkanolammonium salts.

The detergent compositions herein may also contain non-surfactant sudssuppressors. These include, for example: high molecular weighthydrocarbons, N-alkylated amino triazines, monostcaryl phosphates,silicone suds suppressors, secondary alcohols (e.g., 2-alkyl alkanols)and mixtures of such alcohols with silicone oils. Hydrocarbon sudssuppressors are described, for example, in U.S. Pat. No. 4,265,779,issued May 5, 1981 to Gandolfo et al. Silicone suds suppressors are wellknown in the art and are, for example, disclosed in U.S. Pat. No.4,265,779, issued May 5, 1981 to Gandolfo et al and European PatentApplication No. 89307851.9, published Feb. 7, 1990, by Starch, M. S.Mixtures of alcohols and silicone oils are described in U.S. Pat. Nos.4,798,679, 4,075,118 and EP 150,872.

Additional examples of all of the aforementioned suds suppressors may befound in the provisional patent application of Pramod K. Reddy, entitled“Hydrophilic Index for Aqueous, Liquid Laundry Detergent Compositionscontaining LAS”, filed under the Patent Cooperation having P&G Case No.7332P, filed on Nov. 6, 1998 and having Ser. No. 60/107,477, which ishereby incorporated by reference.

The preferred particulate foam control agent used herein contains asilicone antifoam compound, an organic material and a carrier materialonto which the silicone antifoam compound and the organic material aredeposited. The carrier material is preferably a native starch orzeolite. The silicone antifoam compound is selected from the groupconsisting of polydiorganosiloxane, solid silica and mixtures thereof.Preferably, the organic material is selected from:

-   -   (a) at least one fatty acid having a carbon chain containing        from 12 to 20 carbon atoms, said organic material having a        melting point in the range 45° C. to 80° C. and being insoluble        in water;    -   (b) at least one fatty alcohol, having a carbon chain containing        from 12 to 20 carbon atoms, said organic material having a        melting point in the range 45° C. to 80° C. and being insoluble        in water,    -   (c) a mixture of at least one fatty acid and one fatty alcohol,        each having a carbon chain containing from 12 to 20 carbon        atoms, said organic material having a melting point in the range        45° C. to 80° C. and being insoluble in water,    -   (d) an organic material having a melting point in the range        50° C. to 85° C. and comprising a monoester of glycerol and a        fatty acid having a carbon chain containing from 12 to 20 carbon        atoms; and    -   (e) a dispersing polymer; and mixtures thereof.        Preferably, the dispersing polymer is selected from the group        consisting of copolymers of acrylic acid and maleic acid,        polyacrylates and mixtures thereof.

Silicone suds suppressors known in the art which can be used are, forexample, disclosed in U.S. Pat. No. 4,265,779, issued May 5, 1981 toGandolfo et al and European Patent Application No. 89307851.9, publishedFeb. 7, 1990, by Starch, M. S. Silicone defoamers and suds controllingagents in granular detergent compositions arc disclosed in U.S. Pat. No.3,933,672, Bartolotta et al, and in U.S. Pat. No. 4,652,392, Baginski etal, issued Mar. 24, 1987. An exemplary silicone based suds suppressorfor use herein is a suds suppressing amount of a particulate foamcontrol agent consisting essentially of:

-   -   (a) polydimethylsiloxane fluid having a viscosity of from about        20 cs. to about 1,500 cs. at 25° C.;    -   (b) from about 5 to about 50 parts per 100 parts by weight        of (i) of siloxane resin composed of (CH₃)₃ SiO_(1/2) units of        SiO₂ units in a ratio of from (CH₃)₃ SiO_(1/2) units of from        about 0.6:1 to about 1.2: 1; and    -   (c) from about 1 to about 20 parts per 100 parts by weight        of (i) of a solid silica gel.

Additional suds suppressor suitable for use in the present invention aredescribed in greater detail in U.S. Pat. No. 5,762,647, issued June 9,1998, to Brown et al.

(e) Dye Transfer Inhibiting Agents and Other Fabric Care Components—Thecompositions of the present invention may also include one or morematerials effective for inhibiting the transfer of dyes from one fabricto another during the cleaning process. These agents may be includedeither in the nonaqueous surfactant-containing liquid phase or in thesolid particulate material.

Generally, such dye transfer inhibiting agents include polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers ofN-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine,peroxidases, and mixtures thereof. These agents typically comprise fromabout 0.01% to about 10% by weight of the composition, preferably fromabout 0.01% to about 5%, and more preferably from about 0.05% to about2%.

More specifically, the polyamine N-oxide polymers preferred for useherein contain units having the following structural formula: R—A_(X)—P;wherein P is a polymerizable unit to which an N—O group can be attachedor the N—O group can form part of the polymerizable unit or the N—Ogroup can be attached to both units; A is one of the followingstructures: —NC(O)—, —(O)O—, —S—, —O—, —N═; x is 0 or 1; and R isaliphatic, ethoxylated aliphatics, aromatics, heterocyclic or alicyclicgroups or any combination thereof to which the nitrogen of the N—O groupcan be attached or the N—O group is part of these groups. Preferredpolyamine N-oxides are those wherein R is a heterocyclic group such aspyridine, pyrrole, imidazole, pyrrolidine, piperidine and derivativesthereof.

The N—O group can be represented by the following general structures:

wherein R₁, R₂, R₃ are aliphatic, aromatic, heterocyclic or alicyclicgroups or combinations thereof; x, y and z are 0 or 1; and the nitrogenof the N—O group can be attached or form part of any of theaforementioned groups. The amine oxide unit of the polyamine N-oxideshas a pKa<10, preferably pKa<7, more preferred pKa<6.

Any polymer backbone can be used as long as the amine oxide polymerformed is water-soluble and has dye transfer inhibiting properties.Examples of suitable polymeric backbones are polyvinyls, polyalkylenes,polyesters, polyethers, polyamide, polyimides, polyacrylates andmixtures thereof. These polymers include random or block copolymerswhere one monomer type is an amine N-oxide and the other monomer type isan N-oxide. The amine N-oxide polymers typically have a ratio of amineto the amine N-oxide of 10:1 to 1:1,000,000. However, the number ofamine oxide groups present in the polyamine oxide polymer can be variedby appropriate copolymerization or by an appropriate degree ofN-oxidation. The polyamine oxides can be obtained in almost any degreeof polymerization. Typically, the average molecular weight is within therange of 500 to 1,000,000; more preferred 1,000 to 500,000; mostpreferred 5,000 to 100,000.

The most preferred polyamine N-oxide useful in the detergentcompositions herein is poly(4-vinylpyridine-N-oxide) which as an averagemolecular weight of about 50,000 and an amine to amine N-oxide ratio ofabout 1:4. This preferred class of materials can be referred to as“PVNO”.

Further suitable dye transfer inhibitors can be found in U.S. Pat. No.5,466,802, issued Nov. 14, 1995 to Panandiker et al., which is herebyincorporated by reference.

In addition to the dye transfer inhibitors, the present inventionfurther comprises additional agents to provide fabric care benefits. Asdescribed above, these additional agents may be necessary because thehigh concentrations of detergent concentration in the aqueous launderingsolutions used in the present invention may damaged the garments andfabrics contact by the aqueous laundering solutions.

Thus the present invention may also include materials which could beadded to laundry products that would associate themselves with thefibers of the fabrics and textiles laundered using such products andthereby reduce or minimize the tendency of the laundered fabric/textilesto deteriorate in appearance. Any such detergent product additivematerial should, of course, be able to benefit fabric appearance andintegrity without unduly interfering with the ability of the laundryproduct to perform its intended function. Such fabric appearancebenefits can include, for example, improved overall appearance of thelaundered fabrics, reduction of the formation of pills and fuzz,protection against color fading, improved abrasion resistance, etc.

One such fabric care agent which specifically acts to prevent dyes frommigrating from the surface of a garment and into the aqueous launderingsolution but also provides other fabric care benefits is 30polyethyleneimine, PEI 600 E20, having the general formula:

wherein B is a continuation by branching of the polyethyleneiminebackbone. E is an ethyleneoxy unit having the formula:—(CH₂CH₂O)mHwherein m has an average value of about 20. What is meant herein by anaverage value of 20 is that sufficient ethylene oxide or other suitablereagent is reacted with the polyethyleneimine starting material to fullyethoxylate each N—H unit to a degree of 20 ethoxylations. However, thoseskilled in the art will realize that some N—H unit hydrogen atoms willbe replaced by less than 20 ethoxy units and some will be replaced bymore than 20 ethoxy units, therefore, the average of the number ofethoxylations is 20.

The units which make up the polyalkyleneimine backbones are primaryamine units having the formula:H₂N—CH₂CH₂]— and —NH₂which terminate the main backbone and any branching chains, secondaryamine units having the formula:

and which, after modification, have their hydrogen atom substituted byan average of 20 ethyleneoxy units, and tertiary amine units having theformula:

which are the branching points of the main and secondary backbonechains, B representing a continuation of the chain structure bybranching. The tertiary units have no replaceable hydrogen atom and aretherefore not modified by substitution with ethyleneoxy units. Duringthe formation of the polyamine backbones cyclization may occur,therefore, an amount of cyclic polyamine can be present in the parentpolyalkyleneimine backbone mixture. Each primary and secondary amineunit of the cyclic alkyleneimines undergoes modification by the additionof alkyleneoxy units in the same manner as linear and branchedpolyalkyleneimines.

The indices w, x, and y have values such that the average molecularweight of the polyethyleneimine backbone prior to modification is about600 daltons. In addition, those skilled in the art will recognize thateach branch chain must terminate in a primary amine unit, therefore thevalue of the index w is y+1 in the case where no cyclic amine backbonesare present. The average molecular weight for each ethylene backboneunit, —NCH₂CH₂—, is approximately 43 daltons.

The polyamines of the present invention can be prepared, for example, bypolymerizing ethyleneimine in the presence of a catalyst such as carbondioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide,hydrochloric acid, acetic acid, etc. Specific methods for preparingthese polyamine backbones are disclosed in U.S. Pat. No. 2,182,306,Ulrich et al., issued Dec. 5, 1939; U.S. Pat. No. 3,033,746, Mayle etal., issued May 8, 1962; U.S. Pat. No. 2,208,095, Esselmann et al.,issued Jul. 16, 1940; U.S. Pat. No. 2,806,839, Crowther, issued Sep. 17,1957; and U.S. Pat. No. 2,553,696, Wilson, issued May 21, 1951; allherein incorporated by reference.

Other suitable fabric care agents for use in the present detergentcompositions include dye maintenance polymers. One example of such apolymer is the Adduct of Imidazole-epichlorohydrin:

This has a ratio of imidazole:epichlorohydrin of 1.36:1. Further dyemaintenance polymers as well as the Dye Maintenance Parameter Test aredescribed in the copending provisional application of Rajan K.Panandiker et al., entitled “Laundry Detergent Compositions with aCationically Charged Dye Maintenance Polymer,” having P&G Case No. 7488Pand Ser. No. 60/126,074, filed on march 25, 1999, which is herebyincorporated by reference. As described above, these dye maintenancepolymers provide overall fabric care benefits in addition to color careprotection.(f) Thickening, Viscosity Control and/or Dispersing Agents—The detergentcompositions herein may also optionally contain a polymeric materialwhich serves to enhance the ability of the composition to maintain itssolid particulate components in suspension. Such materials may thus actas thickeners, viscosity control agents and/or dispersing agents. Suchmaterials are frequently polymeric polycarboxylates but can includeother polymeric materials such as polyvinylpyrrolidone (PVP) orpolyamide resins.

Polymeric polycarboxylate materials can be prepared by polymerizing orcopolymerizing suitable unsaturated monomers, preferably in their acidform. Unsaturated monomeric acids that can be polymerized to formsuitable polymeric polycarboxylates include acrylic acid, maleic acid(or maleic anhydride), fumaric acid, itaconic acid, aconitic acid,mesaconic acid, citraconic acid and methylenemalonic acid. The presencein the polymeric polycarboxylates herein of monomeric segments,containing no carboxylate radicals such as vinylmethyl ether, styrene,ethylene, etc. is suitable provided that such segments do not constitutemore than about 40% by weight of the polymer.

Particularly suitable polymeric polycarboxylates can be derived fromacrylic acid. Such acrylic acid-based polymers which are useful hereinare the water-soluble salts of polymerized acrylic acid. The averagemolecular weight of such polymers in the acid form preferably rangesfrom about 2,000 to 100,000, more preferably from about 2,000 to 10,000,even more preferably from about 4,000 to 7,000, and most preferably fromabout 4,000 to 5,000. Water-soluble salts of such acrylic acid polymerscan include, for example, the alkali metal, salts. Soluble polymers ofthis type are known materials. Use of polyacrylates of this type indetergent compositions has been disclosed, for example, Diehl, U.S. Pat.No. 3,308,067, issued Mar. 7, 1967. Such materials may also perform abuilder function.

Other suitable polymeric materials suitable for use as thickening,viscosity control and/or dispersing agents include polymers of: castoroil derivatives; polyurethane derivatives, and polyethylene glycol.

If utilized, the optional thickening, viscosity control and/ordispersing agents should be present in the compositions herein to theextent of from about 0.1% to 4% by weight. More preferably, suchmaterials can comprise from about 0.1% to 2% by weight of the detergentscompositions herein.

(g) Clay Soil Removal/Anti-redeposition Agents—The compositions of thepresent invention can also optionally contain water-soluble ethoxylatedamines having clay soil removal and anti-redeposition properties. Ifused, soil materials can contain from about 0.01% to about 5% by weightof the compositions herein.

The most preferred soil release and anti-redeposition agent isethoxylated tetraethylenepentamine. Exemplary ethoxylated amines arefurther described in U.S. Pat. No. 4,597,898, VanderMeer, issued Jul. 1,1986. Another group of preferred clay soil removal-anti-redepositionagents are the cationic compounds disclosed in European PatentApplication 111,965, Oh and Gosselink, published Jun. 27, 1984. Otherclay soil removal/anti-redeposition agents which can be used include theethoxylated amine polymers disclosed in European Patent Application111,984, Gosselink, published Jun. 27, 1984; the zwitterionic polymersdisclosed in European Patent Application 112,592, Gosselink, publishedJul. 4, 1984; and the amine oxides disclosed in U.S. Pat. No. 4,548,744,Connor, issued Oct. 22, 1985. Preferred clay-removing compounds includeethoxylated quaternized amines. Preferred ethoxylated quaternized aminematerials are selected from the group consisting of compounds having thegeneral formula:

wherein each x is independently less than about 16, preferably fromabout 6 to about 13, more preferably from about 6 to about 8, or whereineach x is independently greater than about 35. Materials suitable foruse in the present invention, such as those defined above, can bepurchased from the BASF Corporation in Germany, and the Witco ChemicalCompany.

It has been determined that the degree of ethoxylation is important tothe viscosity of the final detergent compositions described herein.Specifically, for the general structure:

when x is less than about 13 the ethoxylated quaternized amine claymaterials can be added to the present liquid heavy duty detergentcompositions as liquids without causing undesired thickening at lowtemperatures. Likewise, when the degree of ethoxylation for the samestructure is greater than about 35, that is when x is greater than about35, these higher ethoxalated materials can be added to the formulationsas stable solid without melting at high temperatures and without causinglow temperature product thickening.

Of course, it will be appreciated that other, conventional opticalbrightener types of compounds can optionally be used in the presentcompositions to provide conventional fabric “brightness” benefits,rather than a true dye transfer inhibiting effect. Such usage isconventional and well-known to detergent formulations.

Other clay soil removal and/or anti-redeposition agents known in the artcan also be utilized in the compositions herein. Another type ofpreferred anti-redeposition agent includes the carboxy methyl cellulose(CMC) materials. These materials are well known in the art.

(h) Liquid Bleach Activators—The detergent compositions herein may alsooptionally contain bleach activators which are liquid in form at roomtemperature and which can be added as liquids to the liquid phase of thedetergent compositions herein. One such liquid bleach activator isglycerol triacetate, which serves as a solvent in the composition duringstorage but when released into the wash water solution is peroxidizedand functions as a bleach activator. Other examples of bleach activatorsinclude acetyl triethyl citrate (ATC) and nonanoyl valerolactam. Liquidbleach activators can be dissolved in the liquid phase of thecompositions herein.(i) Brighteners, Dyes and/or Perftimes—The detergent compositions hereinmay also optionally contain conventional brighteners, bleach catalysts,dyes and/or perfume materials. Such brighteners, silicone oils, bleachcatalysts, dyes and perfumes must, of course, be compatible andnon-reactive with the other composition components in the aqueous ornon-aqueous liquid environment. If present, brighteners, dyes and/orperfumes will typically comprise from about 0.0001% to 2% by weight ofthe compositions herein.(j) Structure Elasticizing Agents—The liquid detergent compositionsherein can also contain from about 0.1% to 5%, preferably from about0.1% to 2% by weight of a finely divided, solid particulate materialwhich can include silica, e.g., fumed silica, titanium dioxide,insoluble carbonates, finely divided carbon, SD-3 bentone, clays, orcombinations of these materials. Clays are well known to those skilledin the art and are commercially available from companies such as Rheox.Fine particulate material of this type functions as a structureelasticizing agent in the products of this invention. Such material hasan average particle size ranging from about 7 to 40 nanometers, morepreferably from about 7 to 15 nanometers. Such material also has aspecific surface area which ranges from about 40 to 400 m²/g.

The finely divided elasticizing agent material can improve the shippingstability of the liquid detergent products herein by increasing theelasticity of the surfactant-structured liquid phase without increasingproduct viscosity. This permits such products to withstand highfrequency vibration which may be encountered during shipping withoutundergoing undesirable structure breakdown which could lead tosedimentation in the product.

In the case of titanium dioxide, the use of this material also impartswhiteness to the suspension of particulate material within the detergentcompositions herein. This effect improves the overall appearance of theproduct.

(k) Microspheres—Microspheres may be used in the present invention.Suitable microspheres may be made of one or more water-insolublematerials selected from the group consisting of: polymers; silicaceousmaterials; ceramics and mixtures thereof. For further discussion ofmicrospheres, see “Microencapsulation” in Kirk-Othmer Encyclopedia ofChemical Technology, Third Edition, Volume 16, pages 628-651 (John Wiley& Sons, Inc., 1979), which is hereby incorporated by reference.

Polymer microspheres of the present invention are preferably made of awater-insoluble material selected from the group consisting of:thermoplastics; acylonitrile; methacrylonitrile; polyacrylonitrile;polymethacrylonitrile and mixtures thereof. Silicaceous microspheres ofthe present invention are preferably made of one or more silicaceousmaterials selected from the group consisting of glass. Borosilicateglass is particularly preferred.

Commercially available microspheres are available from Akzo-Nobel ofSweden under the trademark EXPANCEL®; PQ Corp. under the trade names PM6545, PM 6550, PM 7220, PM 7228, EXTENDOSPHERES®, LUXSIL®, Q-CEL®,SPHERICEL®; and Malinckrodt under the trademark ALBUMEX®.

Suitable examples of microspheres and further disclosure onmicrosphere-containing liquid detergents may be found in copendingprovisional patent applications of Broeckx et al., entitled “StableNon-aqueous Liquid Laundry Detergents Comprising Low Density Particles”,having P & G Case No. 7417P, provisional Ser. No. 60/119,555 and filedon Feb. 10, 1999, which is hereby incorporated by reference.

In addition to the types of micospheres discussed above, suitablemicrospheres for use in the present invention may also be made fromwash-water soluble biomaterials (such as starches and proteins) whichare disclosed in greater detail in the copending provisional patentapplication of Sadlowski et al., entitled “Nonaqueous Liquid Detergentwith Wash-water soluble Low-Density Filler Particles”, having P&G CaseNo. 7707P, and filed on Aug. 10, 1999, which is hereby incorporated byreference.

In addition, the microspheres used in the present invention may be usedas the core of a particle which is formed by substantially encapsulatingthe core with detergent components. A non-exclusive list of suchcomponents includes organic and inorganic builder material, alkalinitysource material and other coating components. These coated microspheresare disclosed with greater specificity in the copending provisionalpatent application of Aouad et al., entitled “Nonaqueous LiquidDetergent with Wash-water soluble Low-Density Filler Particles”, havingP&G Case No. 7708P, and filed on Aug. 10, 1999, which is herebyincorporated by reference. Coated microspheres are also discussed in thecopending provisional application of Sadlowski et al, P&G Case No.7707P, incorporated above.

(i) Effervescent—In another preferred embodiment of the presentinvention the tablets further comprises an effervescent.

Effervescency as defined herein means the evolution of bubbles of gasfrom a liquid, as the result of a chemical reaction between a solubleacid source and an alkali metal carbonate, to produce carbon dioxidegas,i.e. C₆H₈O⁷+3NaHCO₃₃ Na₃C⁶H₅O₇+3CO₂+3H₂O

Further examples of acid and carbonate sources and other effervescentsystems may be found in: (Pharmaceutical Dosage Forms: Tablets Volume 1Page 287 to 291).

An effervescent may be added to the tablet mix in addition to thedetergent ingredients. The addition of this effervescent to thedetergent tablet improves the disintegration time of the tablet. Theamount will preferably be between 5 and 20% and most preferably between10 and 20% by weight of the tablet. Preferably the effervescent shouldbe added as an agglomerate of the different particles or as a compact,and not as separated particles.

Due to the gas created by the effervescency in the tablet, the tabletcan have a higher D.F.S. and still have the same disintegration time asa tablet without effervescency. When the D.F.S. of the tablet witheffervescency is kept the same as a tablet without, the disintegrationof the tablet with effervescency will be faster.

Further dispersion aid could be provided by using compounds such assodium acetate or urea. A list of suitable dispersion aid may also befound in Pharmaceutical Dosage Forms: Tablets, Volume 1, Second edition,Edited by H. A. Lieberman et all, ISBN 0-8247-8044-2.

The effervescent system may comprise and acid and a base, such as citricacid and sodium bicarbonate, and/or the effervescent system may comprisean enzyme, such as catalase and/or peroxidase and a source of peroxide,such as hydrogen peroxide.

(m) Binders—Non gelling binders can be integrated to the particlesforming the tablet in order to further facilitate dispersion.

If non gelling binders are used, suitable non-gelling binders includesynthetic organic polymers such as polyethylene glycols,polyvinylpyrrolidones, polyacrylates and water-soluble acrylatecopolymers. The handbook of Pharmaceutical Excipients second edition,has the following binders classification: Acacia, Alginic Acid,Carbomer, Carboxymethylcellulose sodium, Dextrin, Ethylcellulose,Gelatin, Guar gum, Hydrogenated vegetable oil type I, Hydroxyethylcellulose, Hydroxypropyl methylcellulose, Liquid glucose, Magnesiumaluminum silicate, Maltodextrin, Methylcellulose, polymethacrylates,povidone, sodium alginate, starch and zein. Most preferable binders alsohave an active cleaning function in the laundry wash such as cationicpolymers, i.e. ethoxylated hexamethylene diamine quaternary compounds,bishexamethylene triamines, or others such as pentaamines, ethoxylatedpolyethylene amines, maleic acrylic polymers.

Non-gelling binder materials are preferably sprayed on and hence have anappropriate melting point temperature below 90° C., preferably below 70°C. and even more preferably below 50° C. so as not to damage or degradethe other active ingredients in the matrix. Most preferred arenon-aqueous liquid binders (i.e. not in aqueous solution) which may besprayed in molten form. However, they may also be solid bindersincorporated into the matrix by dry addition but which have bindingproperties within the tablet.

Non-gelling binder materials are preferably used in an amount within therange from 0.1 to 15% of the composition, more preferably below 5% andespecially if it is a non laundry active material below 2% by weight ofthe tablet.

It is preferred that gelling binders, such as nonionic surfactants areavoided in their liquid or molten form. Nonionic surfactants and othergelling binders are not excluded from the compositions, but it ispreferred that they be processed into the detergent tablets ascomponents of particulate materials, and not as liquids.

(n) Clays—The clay minerals used to provide the softening properties ofthe instant compositions can be described as expandable, three-layerclays, i.e., alumino-silicates and magnesium silicates, having an ionexchange capacity of at least 50 meq/100 g. of clay. The term“expandable” as used to describe clays relates to the ability of thelayered clay structure to be swollen, or expanded, on contact withwater. The three-layer expandable clays used herein are those materialsclassified geologically as smectites.

There are two distinct classes of smectite-type clays; in the first,aluminum oxide is present in the silicate crystal lattice; in the secondclass of smectites, magnesium oxide is present in the silicate crystallattice. The general formulas of these smectites are Al₂(Si₂O₅)₂(OH)₂and Mg₃(Si₂O₅) (OH)₂ for the aluminum and magnesium oxide type clay,respectively. It is to be recognised that the range of the water ofhydration in the above formulas can vary with the processing to whichthe clay has been subjected. This is immaterial to the use of thesmectite clays in the present invention in that the expandablecharacteristics of the hydrated clays are dictated by the silicatelattice structure. Furthermore, atom substitution by iron and magnesiumcan occur within the crystal lattice of the smectites, while metalcations such as Na+, Ca++, as well as H+, can be co-present in the waterof hydration to provide electrical neutrality. Except as notedhereinafter, such cation substitutions are immaterial to the use of theclays herein since the desirable physical properties of the clays arenot substantially altered thereby.

The three-layer, expandable alumino-silicates useful herein are furthercharacterised by a dioctahedral crystal lattice, while the expandablethree-layer magnesium silicates have a trioctahedral crystal lattice.

As noted herein above, the clays employed in the compositions of theinstant invention contain cationic counterions such as protons, sodiumions, potassium ions, calcium ion, magnesium ion, and the like. It iscustomary to distinguish between clays on the basis of one cationpredominantly or exclusively absorbed. For example, a sodium clay is onein which the absorbed cation is predominantly sodium. Such absorbedcations can become involved in exchange reactions with cations presentin aqueous solutions. A typical exchange reaction involving asmectite-type clay is expressed by the following equation:smectite clay (Na)+NH₄OH_smectite clay (NH₄)+NaOH.

Since in the foregoing equilibrium reaction, one equivalent weight ofammonium ion replaces an equivalent weight of sodium, it is customary tomeasure cation exchange capacity (sometimes termed “base exchangecapacity”) in terms of milliequivalents per 100 g. of clay (meq./100g.). The cation exchange capacity of clays can be measured in severalways, including by electrodialysis, by exchange with ammonium ionfollowed by titration or by a methylene blue procedure, all as fully setforth in Grimshaw, “The Chemistry and Physics of Clays”, pp. 264-265,Interscicnce (1971). The cation exchange capacity of a clay mineralrelates to such factors as the expandable properties of the clay, thecharge of the clay, which, in turn, is determined at least in part bythe lattice structure, and the like. The ion exchange capacity of claysvaries widely in the range from about 2 meq/100 g, for kaolinites toabout 150 meq/100 g., and greater, for certain clays of themontmorillonite variety. Illite clays have an ion exchange capacitysomewhere in the lower portion of the range, i.e., around 26 meq/100 g.for an average illite clay.

Illite and kaolinite clays, with their relatively low ion exchangecapacities, are preferably not used as the clay in the instantcompositions. Indeed, such illite and kaolinite clays constitute a majorcomponent of clay soils and, as noted above, are removed from fabricsurfaces by means of the instant compositions. However, smectites, suchas nontonite, having an ion exchange capacity of around 70 meq/100 g.,and montmorillonite, which has an ion exchange capacity greater than 70meq/100 g., have been found to be useful in the instant compositions inthat they are deposited on the fabrics to provide the desired softeningbenefits. Accordingly, clay minerals useful herein can be characterisedas expandable, three-layer smectite-type clays having an ion exchangecapacity of at least about 50 meq/100 g.

While not intending to be limited by theory, it appears thatadvantageous softening (and potentially dye scavenging, etc.) benefitsof the instant compositions are obtainable and are ascribable to thephysical characteristics and ion exchange properties of the clays usedtherein. That is to say, experiments have shown that non-expandableclays such as the kaolinites and the illites, which are both classes ofclays having an ion exchange capacities below 50 meq/100 g., do notprovide the beneficial aspects of the clays employed in the instantcompositions.

The smectite clays used in the compositions herein are all commerciallyavailable. Such clays include, for example, montmorillonite,volchonskoite, nontronite, hectorite, saponite, sauconite, andvermiculite. The clays herein are available under various tradenames,for example, Thixogel #1 and Gelwhite GP from Georgia Kaolin Co.,Elizabeth, New Jersey; Volclay BC and Volclay #325, from AmericanColloid Co., Skokie, Illinois; Black Hills Bentonite BH450, fromInternational Minerals and Chemicals; and Veegum Pro and Veegum F, fromR. T. Vanderbilt. It is to be recognised that such smectite-typeminerals obtained under the foregoing tradenames can comprise mixturesof the various discrete mineral entities. Such mixtures of the smectiteminerals are suitable for use herein.

While any of the smectite-type clays having a cation exchange capacityof at least about 50 meq/100 g. are useful herein, certain clays arepreferred. For example, Gelwbite GP is an extremely white form ofsmectite clay and is therefore preferred when formulating white granulardetergent compositions. Volclay BC, which is a smectite-type claymineral containing at least 3% of iron (expressed as Fe₂O₃) in thecrystal lattice, and which has a very high ion exchange capacity, is oneof the most efficient and effective clays for use in laundrycompositions and is preferred from the standpoint of productperformance.

Appropriate clay minerals for use herein can be selected by virtue ofthe fact that smectites exhibit a true 14 Å x-ray diffraction pattern.This characteristic pattern, taken in combination with exchange capacitymeasurements performed in the manner noted above, provides a basis forselecting particular smectite-type minerals for use in the granulardetergent compositions disclosed herein.

The clay is preferably mainly in the form of granules, with at least 50%(and preferably at least 75% or at least 90%) being in the form ofgranules having a size of at least 100 mm up to 1800 mm, preferably upto 1186 mm, preferably 150-850 mm. Preferably the amount of clay in thegranules is at least 50%, usually at least 70% or 90%, of the weight ofthe granules.

-   (O) Flocculants—Most clay flocculating polymers are fairly long    chained polymers and co-polymers derived from such monomers as    ethylene oxide, acrylamide, acrylic acid, dimethylamino ethyl    methacrylate, vinyl alcohol, vinyl pyrrolidone and ethylene imine.    Gums, like guar gum, are suitable as well.

Preferred are polymers of ethylene oxide, acrylamide or acrylic acid.These polymers dramatically enhance the deposition of a fabric softeningclay if their molecular weights are in the range of from 100 000 to 10million. Preferred are such polymers having a weight average molecularweight of from 150000 to 5 million.

The most preferred polymer is poly (ethylene oxide). Molecular weightdistributions can be readily determined using gel permeationchromatography, against standards of poly (ethylene oxide) of narrowmolecular weight distributions.

The amount of flocculant is preferably 0.5-10% by weight of the tablet,most preferably about 2 to 6%.

The flocculant is preferably mainly in the form of granules, with atleast 50% by weighty (and preferably at least 75% and most preferably atleast 90%) being in the form of granules having a size of at least 100mm up to 1800 mm, preferably up to 1180 mm and most preferably 150-850mm. Preferably the amount of flocculant in the granules is at least 50%,generally at least 70% or 90%, of the weight of the granules.

Other components which are commonly used in detergent compositions andwhich may be incorporated into the detergent tablets of the presentinvention include chelating agents, soil release agents, soilantiredeposition agents, dispersing agents, brighteners, sudssuppressors, fabric softeners, dye transfer inhibition agents andperfumes.

It should be noted that when a clay material is compressed prior toincorporation into a tablet or in a cleaning composition, improveddisintegration or dispensing is achieved. For example, tabletscomprising clay which is compressed prior to incorporation into atablet, disintegrate more rapidly than tablets comprising the same claymaterial which has not been compressed prior to incorporation into atablet. In particular the amount of pressure used for the compression ofthe clay is of importance to obtain clay particles which aiddisintegration or dispensing.

Further, when softening clays are compressed and then incorporated incleaning compositions or tablets, not only improved disintegration ordispensing is obtained, but also good softening of the fabrics.Preferably, the clay component is obtained by compression of a claymaterial.

A preferred process comprises the steps of submitting the clay materialto a pressure of at least 10 MPa, or even at least 20 MPa or even 40MPa. This can for example be done by tabletting or roller compaction ofa clay material, optionally together with one or more other ingredients,to form a clay tablet or sheet, preferably followed by size reduction,such as grinding, of the compressed clay sheet or tablet, to formcompressed clay particles. The particles can then be incorporated in atablet or cleaning composition.

Tabletting methods and roller compaction methods are known in the art.For example, the compression of the clay can be done in a Lloyd 50Ktablet press or with a Chilsonator roller compaction equipment,available form Fitzpatrick Company.

In order to make the present invention more readily understood,reference is made to the following example, which is intended to beillustrative only and not intended to be limiting in scope.

The following examples are presented for illustrative purposes only andare not to be construed as limiting the scope of the appended claims inany way.

Abbreviations Used in Examples

In the detergent compositions, the abbreviated component identificationshave the following meanings:

LAS: Sodium linear C11-13 alkyl benzene sulfonate TAS: Sodium tallowalkyl sulfate C45AS: Sodium C14-C15 alkyl sulfate C45E3S: Sodium C14-C15alkyl sulfate condensed with 3 moles of ethylene oxide QAS:R2.N+(CH3)2(C2H4OH) with R2 = C12-C14 Soap: Sodium linear alkylcarboxylate derived from an 80/20 mixture of tallow and coconut fattyacids Zeolite A: Hydrated sodium aluminosilicate of formulaNa12(AlO2SiO2)12.27H2O having a primary particle size in the range from0.1 to 10 micrometers (weight expressed on an anhydrous basis) NaSKS-6:Crystalline layered silicate of formula d-Na2Si2O5 Citric Anhydrouscitric acid acid: Carbonate: Anydrous sodium carbonate with a particlesize between 200 μm and 900 μm Bicarb- Anhydrous sodium bicarbonate witha particle size onate: distribution between 400 μm and 1200 μm Silicate:Amorphous sodium silicate (SiO2:Na2O = 2.0:1) Sulfate: Anhydrous sodiumsulfate Mg Anhydrous magnesium sulfate sulfate: Citrate: Tri-sodiumcitrate dihydrate of activity 86.4% with a particle size distributionbetween 425 μm and 850 μm MA/AA: Copolymer of 1:4 maleic/acrylic acid,average molecular weight about 70,000 AA: Sodium polyacrylate polymer ofaverage molecular weight 4,500 CMC: Sodium carboxymethyl celluloseProtease: Proteolytic enzyme, having 4% by weight of active enzyme, asdescribed in WO 95/10591, sold by Genencor Int. Inc. Cellulase:Cellulytic enzyme, having 0.23% by weight of active enzyme, sold by NOVOIndustries A/S under the tradename Carezyme Amylase: Amylolytic enzyme,having 1.6% by weight of active enzyme, sold by NOVO Industries A/Sunder the tradename Termamyl 120T Lipase: Lipolytic enzyme, having 2.0%by weight of active enzyme, sold by NOVO Industries A/S under thetradename Lipolase Perborate: Sodium perborate Percar- Sodiumpercarbonate bonate: NOBS: Nonanoyloxybenzene sulfonate in the form ofthe sodium salt NAC- (6-nonamidocaproyl) oxybenzene sulfonate OBS: TAED:Tetraacetylethylenediamine DTPA: Diethylene triamine pentaacetic acidEDDS: Ethylenediamine-N,N′-disuccinic acid, (S,S) isomer in the form ofits sodium salt. Photo- Sulfonated zinc phthlocyanine encapsulated inbleach activated: (1) dextrin soluble polymer CHDM: 1,4CycloHexaneDiMethanol Bright- Disodium4,4′-bis(4-anilino-6-morpholino-1.3.5-triazin-2-yl) ener: amino)stilbene-2:2′-disulfonate HEDP: 1,1-hydroxyethane diphosphonic acidPEGx: Polyethylene glycol, with a molecular weight of x (typically4,000) QEA: bis((C2H5O)(C2H4O)n)(CH3)-N+-C6H12-N+-(CH3)bis((C2H5O)-(C2H4O))n, wherein n = from 20 to 30 SRP: Diethoxylated poly(1, 2 propylene terephtalate) short block polymer SiliconePolydimethylsiloxane foam controller with antifoam: siloxane-oxyalkylenecopolymer as dispersing agent with a ratio of said foam controller tosaid dispersing agent of 10:1 to 100:1In the following examples all levels are quoted as % by weight of thecomposition:

LIQUID PRODUCT FORMULATION EXAMPLES Example I

Nonaqueous liquid detergent compositions comprising a surfactant-richliquid phase and a solid phase were prepared as follows:

%, By weight Composition A Composition B Nonionic Surfactant 21.27 20.14BPP Solvent 18.30 17.33 LAS Surfactant 15.83 14.99 Ethoxylatedquaternized 1.29 1.22 amine clay material Hydrotrope 4.80 0.00Na-Citrate dihydrate 6.73 6.37 Na-Carbonate 9.89 9.37 Bleach Activator5.94 5.62 Sodium Perborate 11.87 11.24 EDDS 1.17 1.11 Duramyl Enzyme0.79 0.87 Carezyme Enzyme 0.03 0.03 Protease Enzyme 0.79 0.75Antifoaming Agents 0.61 0.85 Plastic Microspheres 0.51 0.49 Titaniumdioxide 0.50 0.47 Brightener 0.20 0.19 PEG 8000 0.40 0.38 Perfume 1.721.63 Miscellaneous 2.16 2.15

Liquid detergent composition A is prepared according to the presentinvention and thus contains the preferred hydrotrope 1,4 Cyclo Hexane DiMethanol. As can be seen above, liquid detergent composition B is nearlyidentical to composition A, except that composition B contains none ofthe hydrotrope and its other components have been slightly rebalanced.

The benefits of the hydrotropes discussed herein can be readily seenthrough an experimental test which measures the rate of dissolution of aliquid detergent composition in water.

Rate of Liquid Detergent Product Dissolution in Water Test

-   -   1. Fill a glass beaker with 3 liters of deionised water at        approximately 25° C.    -   2. Insert a 5 cm magnetic stirbar and a conductivity electrode        into the water. Begin mixing the water rate at a rate of 400 rpm        and maintain this constant rate throughout the experiment.    -   3. Place an 85 ml-capacity screen cup with a 60 mesh screen on        the surface of the water and in the center of the beaker in such        a way so that the top of the cup is just above the water and no        water can come in from the top side, only through the screen.    -   4. Very slowly add 1 ml of the liquid detergent product (via a        syringe) into the middle of the screen cup. This is T₀. Measure        the conductivity at T₀.    -   5. Repeat the measurement of the electrical conductivity of the        detergent product-water mixture at regular intervals, such as        after 0.5, 1, 2, 4, 6 and 10 minutes.    -   6. After a suitable amount of time (e.g. 10 minutes) the liquid        detergent product that remains inside the screen cap is added to        the product-water mixture by immersing the cap into the mixture        and increasing the rate of stirring.    -   7. When all of the product has been dissolved and the        conductivity has reached a steady-state value, said value is        recorded.

Both of these compositions were tested using the “Rate of LiquidDetergent Product Dissolution in Water Test” described in great detailabove. The conductivity was measured by electrode immersed in the waterat the beginning of the test-detergent composition solution and the % ofdissolution by and converted into The following results were obtained:

Composition A Composition B Time Conductivity % Dissolution Conductivity% Dissolution  0 s (T₀) 0 0 0 0  30 s 28 19 12 7  60 s 40 27 17 10 120 s54 37 23 14 180 s 62 42 31 18 240 s 68 47 39 23 360 s 78 53 44 26 600 s81 55 49 29 660 s 91 62 51 30

After 11 minutes, full dissolution of the detergent composition wasforced by high agitation and the conductivity measured:

Full 100 100 146 100 Dissolution

The dissolution values were obtained by dividing the measuredconductivity at each individual time by the measured conductivity atfull dissolution and multiplying by 100.

Example II

An aqueous liquid detergent composition according to the presentinvention is prepared as follows:

Composition C Component Wt. % C₁₂₋₁₅ alkyl ether (2.5) sulfate 18.0C₁₂₋₁₃ alkyl ethoxylate (9.0) 2.00 C₁₂₋₁₄ glucose amide 3.50 Citric Acid3.00 C₁₂₋₁₄ Fatty Acid 2.00 CHDM 5.00 MEA to pH 8 Ethanol 3.0Propanediol 6.0 Dye, Perfume, Brighteners, Enzymes, Preservatives, SudsBalance Suppressor, Other Minors, Water 100%

Example III

Nonaqueous liquid detergent compositions comprising a surfactant-richliquid phase and a solid phase were prepared as follows:

%, By weight Com- Com- Com- Com- Com- posi- posi- posi- posi- posi- tiontion tion tion tion A B C D E NaLAS 14.6 14.9 13.9 13.0 14.9 HLAS 0.00.0 1.0 1.9 0.0 Nonionic Surfactant 20.6 20.7 20.7 20.7 20.7 NaCitratedihydrate 3.3 3.3 3.3 3.3 3.3 Copolymer of Acrylic 2.9 2.9 2.9 2.9 2.9Acid and Maleic Acid EDDS 1.2 1.2 1.2 1.2 1.2 Ethoxylated Quarternized1.3 1.3 1.2 1.3 1.3 amine clay material Sodium Perborate 11.5 11.5 11.511.5 11.5 Bleach Activator 2.9 5.8 2.9 2.9 2.9 Triacetin 12.5 0.0 12.512.5 8.7 NaCarbonate 9.6 9.6 9.6 9.6 9.6 BPP Solvent 9.1 17.8 9.1 9.112.0 Hydrotrope 3.8 4.8 3.8 3.8 4.8 Acetic acid 0.2 0.0 0.1 0.0 0.0Protease Enzyme 0.8 0.8 0.8 0.8 0.8 Duramyl Enzyme 0.8 0.4 0.4 0.4 0.4Mannanase Enzyme 0.2 0.2 0.2 0.2 0.2 Carezyme Enzyme 0.1 0.0 0.0 0.0 0.0Brightener 0.2 0.2 0.2 0.2 0.2 Titanium Dioxide 0.5 0.5 0.5 0.5 0.5 PEG8000 0.5 0.5 0.5 0.5 0.5 Perfume 1.7 1.7 1.7 1.7 1.7 Silicone 0.7 0.70.7 0.7 0.7 Silicone surfactant DC 0.3 0.3 0.3 0.3 0.3 3225 Sodium saltof a 0.5 0.5 0.5 0.5 0.5 hydrogenated C16-18 fatty acid MiscellaneousBAL- BAL- BAL- BAL- BAL- ANCE ANCE ANCE ANCE ANCE

GRANULAR/POWDER PRODUCT FORMULATION EXAMPLES Example I

The following compositions are in accordance with the invention.

A B C D E F G H I Spray-dried Granules LAS 10.0 10.0 15.0 5.0 5.0 10.0 —— — QAS 1.0 1.0 — — — DTPA, HEDP and/or EDDS 0.3 0.3 0.5 0.3 — — — MgSO40.5 0.5 0.1 — — — — Sodium citrate — — — 3.0 5.0 — — — Sodium carbonate10.0 10 15 10 7 10 — — — Sodium sulphate 5.0 5.0 — — 5.0 3.0 — — —Sodium silicate 1.6R — — — — 2.0 — — — Zeolite A 16.0 18.0 20.0 20.0 — —— — — SKS-6 — — — 3.0 5.0 — — — — MA/AA or AA 1.0 2.0 11.0 — — 2.0 — — —CHDM 0.5 2.0 2.5 1.5 4.0 1.0 — — — QEA 1.0 — — — 1.0 — — — — Brightener0.05 0.05 0.05 — 0.05 — — — — Silicone oil 0.01 0.01 0.01 — — 0.01 — — —Agglomerate LAS — — — — 0.2 0.2 0.01 C₄₅AS — — — — 2.0 — 1.0 AE₃ — — — —— 1.0 0.5 Carbonate — — 4.0 1.0 1.0 1.0 — Sodium citrate — — — — — — 5.0CFAA — — — — — Citric acid — — — 4.0 — 1.0 1.0 QEA — — — 2.0 2.0 1.0 —SRP — — — 1.0 1.0 0.2 — Zeolite A — — — 15.0 26.0 15.0 16.0 Sodiumsilicate — — — — — — — CHDM — — — — — — 3.0 — — Builder AgglomeratesSKS-6 6.0 — — — 6.0 3.0 — 7.0 10.0 LAS 4.0 5.0 — — 5.0 3.0 — 10.0 12.0Dry-add particulate components Malic acid/carbonate/bicarbonate 8.0 —10.0 4.0 — 8.0 — — 4.0 (40:20:40) QEA — — — 0.2 0.5 — — — — NACAOBS 3.0— — 1.5 — — — 2.5 — NOBS — 3.0 3.0 — — — — — 5.0 TAED 2.5 — — 1.5 2.56.5 — 1.5 — LAS (flake) 10.0 10.0 — — — — — 8.0 — Spray-on Brightener0.2 0.2 0.3 0.1 0.2 0.1 — 0.6 — Dye — — — 0.3 0.05 0.1 — — — AE7 — — — —— 0.5 — 0.7 — Perfume — — — 0.8 — 0.5 — 0.5 — Dry-add Citrate — — 20.04.0 — 5.0 15.0 — 5.0 Percarbonate 15.0 3.0 6.0 10.0 — — — 18.0 5.0Perborate — — — — 6.0 18.0 — — — Photobleach 0.02 0.02 0.02 0.1 0.05 —0.3 — 0.03 Enzymes (cellulase, 1.3 0.3 0.5 0.5 0.8 2.0 0.5 0.16 0.2amylase, protease, lipase) Carbonate 0.0 10.0 — — — 5.0 8.0 10.0 5.0Perfume (encapsulated) 0.6 0.5 0.5 — 0.3 0.5 0.2 0.1 0.6 Suds suppressor1.0 0.6 0.3 — 0.10 0.5 1.0 0.3 1.2 Soap 0.5 0.2 0.3 3.0 0.5 — — 0.3 —Citric acid — — — 6.0 6.0 — — — 5.0 Dyed carbonate (blue, green) 0.5 0.51.0 2.0 — 0.5 0.5 0.5 1.0 SKS-6 — — — 4.0 — — — 6.0 — Fillers up to 100%The compositions exemplified above have at least 90% by weight ofparticles having a geometric mean particle diameter of from about 850microns with a geometric standard deviation of from about 1.2.Unexpectedly, the compositions have improved aesthetics, flowability andsolubility.

TABLET PRODUCT FORMULATION EXAMPLES Example 1a

-   i) A detergent base powder of composition A (see table 1) was    prepared as follows: all the particulate materials of base    composition A were mixed together in a mixing drum to form a    homogenous particulate mixture.-   ii) I part of polyethyleneglycol was sprayed onto 99 parts of base    powder of composition A while mixing.-   iii) Tablets were then made the following way. 54 g of the mixture    was introduced into a mould of circular shape with a diameter of 5.5    cm and compressed at a force of 2.0 kN with an Instron 4464 press.    The tablet tensile strength (or diametrical fracture stress)    obtained at this force was 19.2 kPa. Means to assess tablet strength    (also referred to as diametrical fracture stress) are given in    Pharmaceutical dosage forms: tablets volume 1 Ed. H. A. Lieberman et    al, published in 1989.

Example 1b

-   i) The same composition A was prepared following the same process as    in example 1a.-   ii) 0.9 parts of polyethyleneglycol and 0.1 part of 1,4    cyclohexanedimethanol were mixed together and sprayed onto 99 parts    of base powder of composition A while mixing.-   iii) Tablets were then made following the same way as described in    example 1a. The tablet tensile strength (or diametrical fracture    stress) obtained at a force of 2.0 kN was 23.6 kPa.

Examples 2a-3b were prepared in an analogous fashion to the processdescribed above and according to the formulation compositions detailedbelow.

TABLE 1 Compo- Compo- Compo- sition sition sition A B C (%) (%) (%)Anionic agglomerates¹ 34 34 34 Nonionic agglomerates² 9.57 9.57 9.57Layered silicate³ 2.7 1.5 1.5 Sodium percarbonate 12.43 12.43 12.43Bleach activator agglomerates⁴ 6.48 6.48 6.48 Sodium carbonate 19.0118.96 18.46 EDDS/Sulphate particle⁵ 0.50 0.50 0.50 Tetrasodium salt ofHydroxyethane 0.8 0.8 0.8 Diphosphonic acid Fluorescer 0.11 0.11 0.11Zinc Phthalocyanine sulphonate encapsulate⁶ 0.027 0.027 0.027 Soappowder 1.49 0.74 0.74 Suds suppressor⁷ 1.8 1.8 1.8 Citric acid 7.51 7.517.51 Protease 0.8 0.8 0.8 Cellulase 0.16 0.16 0.16 Amylase 0.61 0.610.61 Polyethylene glycol MW of 4000 flakes — 1.5 1.5 Sodium salt ofLinear Alkyl Benzene 1 1 1.5 Sulphonate/DiIsoPropylBenzeneSulphonate⁸¹Anionic agglomerates comprise 37% anionic surfactant, 2% cationicsurfactant, 22% layered silicate, 10% acetate, 6% carbonate and 23%zeolite. ²Nonionic agglomerates comprise of 24% nonionic surfactant, 6%ethoxylated hexamethylene diaminequat, 40% acetate/zeolite mix, 20%carbonate and 10% zeolite. ³Layered silicate comprises of 95% SKS 6 and5% silicate. ⁴Bleach activator agglomerates comprise of 81% TAED, 17%acrylic/maleic copolymer (acid form) and 2% water. ⁵Ethylene diamineN,N-disuccinic acid sodium salt/Sulphate particle comprise of 58% ofEthylene diamine N,N-disuccinic acid sodium salt, 23% of sulphate and19% water. ⁶Zinc phthalocyanine sulphonate encapsulates are 10% active.⁷Suds suppressor comprises of 11.5% silicone oil (ex Dow Corning); 59%of zeolite and 29.5% of water. ⁸Sodium salt of Linear Alkyl BenzeneSulphonate/DiIsoPropylBenzeneSulphonate comprises of 67% Linear AlkylBenzene Sulphonate and 33% DiIsoPropylBenzeneSulphonate.

A tablet binder composition was sprayed onto the above detergent basepowders according to the following compositions:

TABLE 2 Ex- Ex- Ex- Ex- Ex- Ex- ample ample ample ample ample ample 1a1b 2a 2b 3a 3b Powder A 99% 99% Powder B 98.5% 98.5% Powder C 98.5%98.5% Polyethylene- 1% 0.9% 1.50% 1.35% 1.5% 1.3% glycol 1,4 0.1% 0.15%0.2% cyclohexane- dimethanol

The strength of the tablets was then tested as has been described abovein step iii) and elsewhere in the present invention:

TABLE 3 Ex- Ex- Ex- Ex- Ex- Ex- ample ample ample ample ample ample 1a1b 2a 2b 3a 3b Tablet tensile 19.2 23.6 12.4 14.7 16 19 strength (kPa)

The tensile strength of the tablet samples which contained CHDM weregreater than the CHDM tablet samples of virtually identical composition,but which contained no CHDM.

The operating window was also assessed:

TABLE 4 Example 3a Example 3b Density at a tablet hardness of 1035 10105.5 kp Density at a tablet dispensing of 1052 1035 15%The operating window of the tablet samples which contained CHDM(width=25 g/liter) was broader than the operating window of the tabletsamples which contained no CHDM (width=17 g/liter).

The amount of dispensing of a detergent tablet as tabulated above intable 4 can be determined through an experimental test which measuresthe amount of detergent product dispensed during an automatic washprocess in the following way:

-   -   1. Two tablets, nominally 50 grams each, are weighed, and then        placed in the dispenser of a Baucklnecht® WA9850 washing        machine. The water supply to the washing machine is set to a        temperature of 20° C. and a hardness of 21 grains per gallon,        the dispenser water inlet flow-rate being set to 8 l/min.    -   2. The level of tablet residues left in the dispenser is checked        by switching the washing on and the wash cycle set to wash        program 4 (white/colors, short cycle).    -   3. The dispensing percentage residue is then determined as        follows:        % dispensing=residue weight×100/original tablet weight

The level of residues is determined by repeating the procedure 10 timesand an average residue level is calculated based on the ten individualmeasurements.

Having thus described the invention in detail, it will be clear to thoseskilled in the art that various changes may be made without departingfrom the scope of the invention and the invention is not to beconsidered limited to what is described in the specification.

1. A non-aqueous liquid laundry detergent composition comprising: A)from about 49% to about 99.95% by weight of the composition of asurfactant-containing non-aqueous liquid phase; and B) from about 1% toabout 50% by weight of the composition of a particulate material whichis substantially insoluble in said liquid phase and which is selectedfrom the group consisting of peroxygen bleaching agents, bleachactivators, organic detergent builders, inorganic alkalinity sources,enzymes, brighteners, polymers and mixtures thereof; and C) a hydrotropewherein the hydrotrope comprises 1, 4 Cyclo Hexane Di Methanol, andwherein the composition comprises no quaternary compounds which arederivatives of any of the following: C₁₆₋₁₈ unsaturated fatty acids,methyl diethanolamine or methyl chloride.
 2. A non-aqueous liquiddetergent composition according to claim 1, wherein the detergentcomposition includes from about 0.01% to about 10% by weight of thecomposition of a fabric care agent.
 3. A non-aqeous liquid detergentcomposition according to claim 1, wherein the surfactant-containingnon-aqueous liquid phase has a density of from about 0.6 to 1.4 g/cc. 4.A non-aqueous liquid detergent composition according to claim 1, whereinthe particulate material has a particle size of from about 0.1 to 1500microns.
 5. A non-aqueous liquid detergent composition according toclaim 1 further comprising microspheres having a median particle size offrom 10 μm to 150 μm.
 6. A non-aqueous liquid detergent compositionaccording to claim 5 comprising microspheres having an average densityof from 0.1 g/ml to 1.8 g/ml.
 7. A method of laundering soiled fabricscomprising contacting said fabric in an aqueous laundering solution witha nonaqueous liquid detergent composition according to claim
 1. 8. Amethod of laundering soiled fabrics comprising contacting said fabricsin an aqueous laundering solution with a non aqueous liquid a detergentcomposition according to claim 2.